Toxicologically acceptable alkylphenol detergents as friction modifiers in automotive lubricating oils

ABSTRACT

The disclosed technology relates to the use of toxicologically acceptable hydrocarbyl- (e.g. alkyl-) phenol detergents and their salts in automotive lubricating oils, such as, for example, automatic or manual transmissions.

BACKGROUND OF THE INVENTION

The disclosed technology relates to the use of toxicologicallyacceptable hydrocarbyl- (e.g. alkyl-) phenol detergents and their saltsin automotive lubricating oils, such as, for example, automatic ormanual transmissions.

Phenol-based detergents are known. Among these are phenates based onphenolic monomers, linked with sulfur bridges or alkylene bridges suchas methylene linkages derived from formaldehyde. The phenolic monomersthemselves are typically substituted with an aliphatic hydrocarbyl groupto provide a measure of oil solubility. The hydrocarbyl groups may bealkyl groups, and, historically, dodecylphenol (or propylenetetramer-substituted phenol) has been widely used. An early reference tobasic sulfurized polyvalent metal phenates is U.S. Pat. No. 2,680,096,Walker et al., Jun. 1, 1954; see also U.S. Pat. No. 3,372,116,Meinhardt, Mar. 5, 1968.

Recently, however, certain alkylphenols and products prepared from themhave come under increased scrutiny due to their association as potentialendocrine disruptive materials. In particular, alkylphenol detergentswhich are based on phenols alkylated with oligomers of propylene,specifically propylene tetramer (or tetrapropenyl), may contain residualalkyl phenol species. There is interest, therefore, in developingalkyl-substituted phenol detergents, for uses in lubricants, fuels, andas industrial additives, which contain a reduced or eliminated amount ofdodecylphenol component and other substituted phenols having propyleneoligomer substituents of 10 to 15 carbon atoms. Nevertheless, it isdesirable that the products should have similar oil-solubilityparameters as phenates prepared from C10-15 propylene oligomers.

There have been several efforts to prepare phenate detergents that donot contain Cn alkyl phenols derived from oligomers of propylene. U.S.Pat. No. 7,435,709, Stonebraker et al., Oct. 14, 2008, discloses alinear alkylphenol derived detergent substantially free of endocrinedisruptive chemicals. It comprises a salt of a reaction product of (1)an olefin having at least 10 carbon atoms, where greater than 90 mole %of the olefin is a linear C20-C30 n-alpha olefin, and wherein less than10 mole % of the olefin is a linear olefin of less than 20 carbon atoms,and less than 5 mole % of the olefin a branched chain olefin of 18carbons or less, and (2) a hydroxyaromatic compound.

U.S. Application 2011/0190185, Sinquin et al, Aug. 4, 2011, discloses anoverbased salt of an oligomerized alkylhydroxyaromatic compound. Thealkyl group is derived from an olefin mixture comprising propyleneoligomers having an initial boiling point of at least about 195° C. anda final boiling point of greater than 325° C. The propylene oligomersmay contain a distribution of carbon atoms that comprise at least about50 weight percent of C14 to C20 carbon atoms.

U.S. Application 2011/0124539, Sinquin et al, May 26, 2011, discloses anoverbased, sulfurized salt of an alkylated hydroxyaromatic compound. Thealkyl substituent is a residue of at least one isomerized olefin havingfrom 15 to about 99 wt. % branching. The hydroxyaromatic compound may bephenol, cresols, xylenols, or mixtures thereof.

U.S. Application 201 1/01 18160, Campbell et al., May 19, 2011,discloses an alkylated hydroxyaromatic compound substantially free ofendocrine disruptive chemicals. An alkylated hydroxyaromatic compound isprepared by reacting a hydroxyaromatic compound with at least onebranched olefinic propylene oligomer having from about 20 to about 80carbon atoms. Suitable hydroxyaromatic compounds include phenol,catechol, resorcinol, hydroquinone, pyrogallol, cresol, and the like.

U.S. Application 2010/0029529, Campbell et al., Feb. 4, 2010, disclosesan overbased salt of an oligomerized alkylhydroxyaromatic compound. Thealkyl group is derived from an olefin mixture comprising propyleneoligomers having an initial boing point of at least about 195° C. and afinal boiling point of no more than about 325° C. Suitablehydroxyaromatic compounds include phenol, catechol, resorcinol,hydroquinone, pyrogallol, cresol, and the like.

U.S. Application 2008/0269351, Campbell et al., Oct. 30, 2008, disclosesan alkylated hydroxyaromatic compound substantially free of endocrinedisruptive chemicals, prepared by reacting a hydroxyaromatic compoundwith a branched olefinic oligomer having from about 20 to about 80carbon atoms. WO/PCT application 2013/059173, Cook et al., discloses anoverbased salt of an oligomerized alkylhydroxyaromatic compound. Thealkyl group is a combination of very short hydrocarbyl group (i.e. 1 to8 carbon atoms) and a long hydrocarbyl group (at least about 25 carbonatoms). Suitable compounds include those made from a mixture ofpara-cresol and polyisobutylene-substituted phenol.

Other general technology includes that of U.S. Pat. No. 6,310,009,Carrick et al., Oct. 30, 2001, which discloses salts of the generalstructure

where R may be an alkyl group of 1 to 60 carbon atoms, e.g., 9 to 18carbon atoms. It is understood that R¹ will normally comprise a mixtureof various chain lengths, so that the foregoing numbers will normallyrepresent an average number of carbon atoms in the R¹ groups (numberaverage).

There is also co-pending application PCT/US2015/031939 to Walker et al.which discloses an alternative alkyl phenol for use as a detergent ininternal combustion engines.

None of the art teaches the use of an alternative alkyl phenol indriveline devices.

SUMMARY OF THE INVENTION

The disclosed technology, therefore, solves the problem of providing atoxicologically acceptable alkylphenol detergent in a driveline deviceby supplying to the device an alkyl phenol as described herein.

One aspect of the disclosed technology is directed to a transmissionlubricant composition. In an embodiment, the transmission lubricant caninclude an oil of lubricating viscosity, from about 0.1 to about 5 wt %of a dispersant, and from about 0.1 to about 5 wt % of a detergent. Thedetergent in the transmission lubricant can include from about 0.01 toabout 2 wt % of an alkylphenol detergent that has at least one unit ofan alkyl-substituted phenol wherein the alkyl group is derived fromoligomers of an olefin compound containing 3 to 8 carbon atoms, whereinthe olefin-derived alkyl group comprises at least 30 mol percent of anolefin with 4 or more carbon atoms.

In an embodiment, the alkylphenol detergent can be a sulfur-bridgedphenate, a sulfur-free alkylene-bridged phenate, a salicylate, ormixtures thereof.

In another embodiment, alkylphenol detergent can include one or morealkali metals, one or more alkaline earth metals, or mixtures thereof.

In a further embodiment, the alkylphenol detergent can be overbased, andin an even further embodiment the overbased alkylphenol detergent canhave a metal ratio of at least 1.5, at least 5, or at least 7.

In an embodiment, the alkyl group of the alkylphenol detergent caninclude oligomers of n-butene, where the alkyl group can be ahydrocarbyl group of 12 to 48 carbon atoms.

In some embodiments, the alkylphenol detergent can be an overbasedsulfur-coupled alkylphenol detergent with a metal ratio of at least 1.5.

In further embodiments, the alkylphenol detergent can include asulfur-bridged phenate represented by the structure

wherein each R can be an aliphatic hydrocarbyl group derived fromoligomers of n-butene, higher alphaolefins, or mixtures thereof, thatcontains 8 to 48 carbon atoms; and n=0 to 8, or 1 to 6, or 1 to 4, or 2to 4.

In embodiments, the alkylphenol detergent can be a neutral or overbasedsalt of alkylsalicylic acid. In some instances, the alkylphenoldetergent can be an alkylsalicylate represented by the structure

where R can be an aliphatic hydrocarbyl group derived from oligomers ofn-butene, higher alphaolefins, or mixtures thereof, and wherein thehydrocarbyl group contains 8 to 48 carbon atoms.

In an embodiment, the oil of lubricating viscosity in the lubricant caninclude comprises at least one API Group I, II, III, IV, or V, lubricantor mixtures thereof.

In some embodiments, the lubricant can additionally include at least oneof a phosphorus-containing antiwear agent comprising a non-ionicphosphorus compound; an amine salt of a phosphorus compound; acalcium-containing detergent; another friction modifier; asulphur-containing extreme pressure agent; a sulphur-containingcorrosion inhibitor; or combinations thereof. In further embodiments,the lubricant can further include from about 0.05 to about 3 wt % of aC₂₋C₁₈ di- or tri-hydrocarbyl phosphite, based on the total weight ofsaid lubricant. In still further embodiments, the lubricant can includeless than 2000 ppm zinc based on the total weight of said lubricant. Insome embodiments, the lubricant can be substantially free of, to freeof, a phenol alkylated with oligomers of propylene.

In another aspect of the technology, there is provided a method oflubricating a manual transmission by supplying the lubricant compositiondescribed herein to said manual transmission. In some embodiments, thelubricant composition can include the oil of lubricating viscosity; athiadiazole; a phosphorous containing antiwear agent; the dispersant;the detergent; and the alkylphenol detergent.

In another aspect of the technology, there is provided a method oflubricating an automatic transmission by supplying the lubricantcomposition described herein to said automatic transmission. In someembodiments, the lubricant composition can include the oil oflubricating viscosity; a thiadiazole; a phosphorous containing antiwearagent; the dispersant; the detergent; and the alkylphenol detergent.

In another aspect of the technology, there is provided a method oflubricating an off-highway vehicle by supplying the lubricantcomposition described herein to said off-highway vehicle. In someembodiments, the lubricant composition can include the oil oflubricating viscosity; a zinc dialkyl dithiophosphate antiwear agent;the dispersant; the detergent and the alkylphenol detergent. In anembodiment, the off-highway vehicle can be a farm-tractor vehicle or aconstruction vehicle.

In another aspect of the technology, there is provided a method oflubricating a highway vehicle by supplying the lubricant compositiondescribed herein to said highway vehicle. In some embodiments, thelubricant composition can include the oil of lubricating viscosity; thedispersant; the detergent (including the alkylphenol detergent); asulfurized olefin; a thiadiazole; and a phosphorous containing antiwearagent.

DETAILED DESCRIPTION OF THE INVENTION

Various preferred features and embodiments will be described below byway of non-limiting illustration. When used herein, the shorthand “wt %”refers to the weight percent of the material referred to based on atotal weight of the composition within which the material is included.

The disclosed technology provides a lubricating composition forautomotive gears, such as transmissions, including an alkylphenoldetergent, as well as methods for lubricating automotive gears and a useas disclosed herein.

One of the materials of the presently disclosed technology may be abridged alkylphenol compound. Such materials in general, their methodsof preparation, and use in lubricants are well known from, for instance,the above-referenced U.S. Pat. No. 2,680,096, Walker et al. They may beprepared starting from alkyl phenol such as alkylphenols derived fromoligomers of n-butene, or mixtures thereof, any of which are readilyavailable as starting materials. The alkylation of phenol and itshomologues is well known, typically by catalyzed reaction of an olefin,often an α-olefm, with phenol (or with salicylic acid or anotherhomologue, as the case may be). Alkylation of phenol is described ingreater detail in the Kirk-Othmer Encyclopedia of Chemical Technology,third edition (1978) vol. 2, pages 82-86, John Wiley and Sons, New York.

Linking of alkyl (or more generally, hydrocarbyl) phenols to formoligomeric species, is also well known. They may be condensed, forinstance, with formaldehyde or with other aldehydes or ketones such asacetone to form methylene (or alkylene) bridged structures, as describedon pages 76-77 of the above cited Kirk-Othmer reference. If condensationwith an aldehyde or ketone is intended, it is desirable that thealdehyde or ketone not be a C12 species, to avoid the formation of anyC12 substituted phenolic materials. In certain embodiments the materialmay be an aldehyde of 8 or fewer carbon atoms, such as 1 to 4, or 1 or2, or a single carbon atom (formaldehyde). The length of the resultingoligomeric chain of phenolic and alkylene units will depend to someextent on the molar ratio of the reactants, as is well known. Thus anequimolar amount of phenol and formaldehyde provides a condensate with arelatively longer oligomeric chain than that obtained when there is astoichiometric excess of one species or the other. Under certainconditions, carbon- and oxygen-containing linkages may also be formed,such as those of the general structure —CH₂—O—CH₂— or homologues inwhich the hydrogens are replaced by alkyl groups. These may be formed bythe condensation of more than a single aldehyde or ketone group. Suchstructures are known, for example, from U.S. Pat. No. 6,310,009, seecol. 2 lines 14-17 and col. 6 lines 1-45. Thus the linking groupsprepared form aldehydes or ketones may be generally described as“carbon-containing” bridging groups, e.g., an alkylene bridge or anether bridge.

Substituted phenols may also be linked together to make sulfur bridgedspecies, which may include bridges of single sulfur atoms (—S—) ormultiple sulfur atoms (e.g., —S_(x)— where x may be 2 to 8, typically 2or 3). Sulfurized phenols may be prepared by reaction with active sulfurspecies such as sulfur monochloride or sulfur dichloride as described onpages 79-80 of the Kirk-Othmer reference or with elemental sulfur, asdescribed, for instance, in U.S. Pat. No. 2,680,096. Sulfurization (withsulfur) may be conducted in the presence of a basic metal compound suchas calcium hydroxide or calcium oxide, thus preparing a metal salt, asdescribed in greater detail, below. Basic sulfurized phenates and amethod for their preparation are also disclosed in U.S. Pat. No.3,410,798, Cohen, Nov. 12, 1968. The examples and claim 1 thereofdisclose a method, comprising reacting at a temperature above about 150°C., (A) a phenol, (B) sulfur, and (C) an alkaline earth base, in thepresence of a promoter comprising (D) about 5-20 mole percent, based onthe amount of component A, of a carboxylic acid or alkali metal,alkaline earth metal, zinc, or lead salt thereof and (E) as a solvent, acompound of the formula R(OR′)_(x)OH, e.g., a polyalkylene glycol. Thephenol (A), in turn, may be a hydrocarbyl-substituted phenol which maybe prepared by mixing a hydrocarbon and a phenol at a temperature ofabout 50-200° C. in the presence of a suitable catalyst such as aluminumtrichloride (col. 2 line 51 of U.S. Pat. No. 3,410,798, and followingtext).

Alkylphenol

In the present technology, the alkyl group is derived from a polyolefincompound comprising n-butene (also referred to as 1-butene) monomers,higher alpha-olefins, or mixtures thereof. In addition to n-butene,suitable alpha-olefins include isobutylene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-nonene, 1-decene, and mixtures thereof. In oneembodiment, the alkyl group of the alkylphenol is a polyolefin compoundcomprising at least 25 mol % 1-butene, at least 50 mol % 1-butene, or atleast 75 mol % 1-butene. In one embodiment, the alkyl group of thealkylphenol consists of oligomers or polymers of 1-butene.

Suitable polyolefins include oligomers or polymers of n-butene. A butenepolymer or oligomer containing 8 to 48 carbon atoms would contain 2 to12 butene monomer units. An n-butene polymer or oligomer containing 12to 32 carbon atoms would contain 3 or 8 n-butene monomer units. Furtherdetails of alkylation are disclosed in the above-cited Kirk-Othmerreference.

The alkylphenol from which the detergent may be derived may becharacterized as a phenol substituted with one or more alkyl groupsderived from a polyolefin or oligomerized olefin as described above. Thealkylphenol may contain one or more alkyl groups derived from anoligomer (or polymer) of n-butene. In one embodiment, the alkylphenolmay be C₈ to C₄₈ alkylphenol, a C₁₂ to C₃₂ alkylphenol, a C₁₆ to C₂₄alkylphenol, or mixtures thereof, wherein the alkyl groups are oligomersof n-butene.

Bridged Phenol Detergents

In certain embodiments, the alkylphenol-containing detergent may be asulfur-bridged phenate detergent, a sulfur-free alkylene-bridged phenatedetergent, or mixtures thereof. Detergents of this type are ionic(usually metal) salts of bridged phenolic compounds. The bridgedphenolic compound material may be represented by the structure

-   -   or more generally

or isomers thereof, wherein each y may be, in the case of formula I, 1but more generally from 1 to 4, especially 1 or 2, and each R may be analiphatic hydrocarbyl group derived from oligomers of n-butene, higheralphaolefins, or mixtures thereof, and wherein the hydrocarbyl groupcontains 8 to 48 carbon atoms. The average number of carbon atoms in allthe R groups, combined, may be 16 to 320 (or 20 to 220, or 24 to 120).The average number of carbon atoms in all R groups, combined, may alsobe from about 16 to about 100 (or 20 to 50, or 24 to 36, or 14 to 20 or18 to 36). Where the bridging group may be listed as “X”, each X may be,independently, a carbon-containing bridge, or an alkylene group, or amethylene group, or a bridge of 1 or more sulfur atoms represented byS_(y), where y may be 1 to 4, especially 1 or 2. In these structures, nmay, in certain embodiments, be 0 to 8, or 1 to 6, or 1 to 4, or 2 to 4.That is, the bridged material may, in these embodiments, contain 2 to 10bridged phenolic groups, or 3 to 7, or 3 to 5, or 4 such groups. Since nmay be zero, it may be evident that throughout this specification, theexpression “oligomeric” may be interpreted to include dimeric species.Accordingly, sometimes the expression “dimeric or oligomeric” may beused to express this concept, which may include, as above, as anexample, 0 to 8 interior units bracketed by [ ]_(n) or 2 to 10 unitsoverall. In certain embodiments, in the above structure, one or two ofthe R groups are aliphatic hydrocarbyl groups containing 30 to 200 or 35to 80 carbon atoms and the remainder of the R groups are methyl groups.

In one embodiment, the sulfur-bridged alkylphenol-containing detergentmay be an oligomer of p-(tetrabutenyl)phenol. A sulfur-bridged oligomerof oligobutenylphenol may be represented by the structure (III)

where n=0 to 4, and m=0 to 7, or for example, from 1 to 3 or 4.

In certain embodiments, the alkylene-bridged phenate detergent may be asaligenin detergent. A saligenin detergent contains a bridged-alkylphenol compound that may be an alkylene coupled alkylphenol representedby the structure (IV)

where each R may be an aliphatic hydrocarbyl group derived fromoligomers of n-butene, higher alphaolefins, or mixtures thereof, andwherein the hydrocarbyl group contains 8 to 48 carbon atoms; where theeach bridging group (X) may be independently a carbon-containing bridge,or a hydrocarbylether linkage (such as —CH₂—O—CH₂—), or an alkylenegroup, or a methylene group; each Y may be independently —CHO or —CH₂OH;wherein the —CHO groups comprise at least about 10 mole percent of the Xand Y groups; and n may be an integer from 1 to 10.

In certain embodiments, the alkylene-bridged phenate detergent may be asalixarate detergent. A salixarate detergent contains a bridged-alkylphenol compound that may be an alkylene coupled alkylphenol that may befurther bridged or coupled to salicylic acid. The bridged phenol of asalixarate may be represented by the structure (V)

where R may be an aliphatic hydrocarbyl group derived from oligomers ofn-butene, higher alphaolefins, or mixtures thereof, and wherein thehydrocarbyl group contains 8 to 48 carbon atoms; where the each bridginggroup (X) may be independently a carbon-containing bridge, or analkylene group, or a methylene group; and n may be an integer from 1 to10

The bridged alkylphenol detergents may be neutral or overbased orsuperbased. Such overbased detergents are generally single phase,homogeneous Newtonian systems characterized by a metal and/or ammoniumcontent in excess of that which would be present for neutralizationaccording to the stoichiometry of the metal or ammonium and theparticular acidic organic compound reacted with the metal or ammoniumcompound. The overbased materials are typically prepared by reacting anacidic material (typically an inorganic acid or lower carboxylic acidsuch as carbon dioxide) with a mixture of bridged alkylphenol compounds(referred to as a substrate), a stoichiometric excess of a metal base,typically in a reaction medium of an one inert, organic solvent (e.g.,mineral oil, naphtha, toluene, xylene) for the acidic organic substrate.Typically also a small amount of promoter such as a phenol or alcohol ispresent, and in some cases a small amount of water. The acidic organicsubstrate will normally have a sufficient number of carbon atoms toprovide a degree of solubility in oil.

In certain embodiments, the overbased bridged-phenol detergent may be ametal-containing detergent, an amine or ammonium containing detergent,or mixtures thereof. In one embodiment the overbased metal-containingdetergent may be zinc, sodium, calcium or magnesium salts of a phenate,sulfur containing phenate, salixarate or saligenin. In one embodiment,the overbased detergent comprises a salt of an alkylamine or quaternaryammonium compound. Overbased salixarates, phenates and saligeninstypically have a total base number (TBN) (by ASTM D2896) of 50 to 600 mgKOH/g, or for example, 70 or 115 to 500 mg KOH/g.

Salicylates

In certain embodiments, the alkylphenol-containing detergent may be analkylsalicylate or salicylate detergent. A salicylate detergent may be aneutral or overbased metal salt of alkylsalicylic acid. Alkyl salicylicacid may be represented by the formula (VI)

where R may be an aliphatic hydrocarbyl group derived from oligomers ofn-butene, higher alphaolefins, or mixtures thereof, and wherein thehydrocarbyl group contains 8 to 48 carbon atoms.

The alkylsalicylate may be a neutral or nearly neutral salt ofalkylsalicylic acid; by nearly neutral, it is meant that there is anexcess of base of no more than 15 mol percent, i.e. if the salt ismetal-containing, the metal ratio is 1.15 or less. In one embodiment theneutral salt of the alkylsalicylic acid may be an amine or ammoniumsalt, a metal salt, or mixtures thereof.

Amines suitable for use in the preparation of the neutral amine saltedalkylsalicylate are not overly limited and may include any alkyl amine,though generally are fatty acid amines derived from fatty carboxylicacids. The alkyl group present in the amine may contain from 10 to 30carbon atoms, or from 12 to 18 carbon atoms, and may be linear orbranched. In some embodiments the alkyl group may be linear andunsaturated. Typical amines include pentadecylamine, octadecylamine,cetylamine, oleylamine, decylamine, dodecylamine, dimethyldodecylamine,tridecylamine, heptadecylamine, octadecylamine, stearylamine, and anycombination thereof. In some embodiments the fatty acid derived aminesalt of an alkylsalicylic acid may be a salt of oleylamine. In certainembodiments, the amine may be a gamma-aminoester compound; aminoestersof this type may be derived from Michael addition of a primary amine toan alkyl diester of itaconic acid represented by the formula

where R¹ and R² are hydrocarbyl groups containing 2 to 30 carbon atoms,and R³ is a hydrocarbyl group containing 4 to 50 carbon atoms. In someembodiments, R³ of the aminoester compound is an alkyl group that has atleast one hydrocarbyl group substituted at the 1-, or 2-position of thealkyl group. In one embodiment, the aminoester is dibutyl2-(((2-ethylhexyl)-amino)methyl)succinate.

In certain embodiments, the neutral salt of the alkylsalicylic acid maybe a quaternary ammonium salt, also referred to as a quaternary nitrogencompound. Quaternary nitrogen compounds are characterized in that thenitrogen atom is four-coordinate; this results in a cationic speciesthat is not protic, i.e. an acidic proton is not released under basicconditions. Quaternary nitrogen compounds may be characterized asfalling into two large groups, four coordinate tetrahydrocarbylammoniumcompounds, for example tetrabutylammonium, and three coordinate aromaticcompounds, for example N-hydrocarbylpyridinium.

In some embodiments the quaternary nitrogen salt may comprise thereaction product of (a) hydrocarbyl-substituted compound having atertiary amino group and (b) a quaternizing agent suitable forconverting the tertiary amino group of (a) to a quaternary nitrogen,wherein the quaternizing agent may be chosen from dialkyl sulfates,benzyl halides, hydrocarbyl substituted carbonates; hydrocarbyl epoxidesin combination with an acid or mixtures thereof. In one embodiment, thequaternary nitrogen salt comprises the reaction product of (i) at leastone compound chosen from: a polyalkene-substituted amine having at leastone tertiary amino group and/or a Mannich reaction product having atertiary amino group; and (ii) a quaternizing agent.

The alkylphenol-containing detergents, be they phenates, saligenins,salixrates, or salicylates, may be metal-containing detergents.Metal-containing detergents may be neutral, or very nearly neutral, oroverbased. An overbased detergent contains a stoichiometric excess of ametal base for the acidic organic substrate. This is also referred to asmetal ratio. The term “metal ratio” is the ratio of the totalequivalents of the metal to the equivalents of the acidic organiccompound. A neutral metal salt has a metal ratio of one. A salt having4.5 times as much metal as present in a normal salt will have metalexcess of 3.5 equivalents, or a ratio of 4.5. The term “metal ratio” isalso explained in standard textbook entitled “Chemistry and Technologyof Lubricants”, Third Edition, Edited by R. M. Mortier and S. T.Orszulik, Copyright 2010, page 219, sub-heading 7.25.

In one embodiment the overbased metal-containing alkylphenol detergentmay be calcium or magnesium overbased detergent. In one embodiment, theoverbased detergent may comprise a calcium alkylphenol detergent with ametal ratio of at least 1.5, at least 3, at least 5, or at least 7. Incertain embodiments, the overbased calcium alkylphenol detergent mayhave a metal ratio of 1.5 to 25, 2.5 to 20 or 5 to 16.

Alternatively, the alkylphenol detergent may be described as having TBN.Overbased phenates and salicylates typically have a total base number of120 to 600 mg KOH/g, or 150 to 550 mg KOH/g, or 180 to 350 mg KOH/g. Theamount of the alkylphenol-containing detergent present in a lubricantcomposition may be defined as the amount necessary to deliver an amount,or range of amounts, of TBN to the lubricant composition. In certainembodiments, the alkylphenol-containing detergent may be present in alubricant composition in amount to deliver 0.5 to 10 TBN to thecomposition, or 1 to 7 TBN, or 1.5 to 5 TBN to the composition.

Overbased detergents may also be defined as the ratio of the neutraldetergent salt, also referred to as detergent soap, and the detergentash. The overbased detergent may have a weight ratio of ash to soap of3:1 to 1:8, or 1.5:1 to 1:4.1, or 1.3:1 to 1:3.4.

The product of the disclosed technology may beneficially be used as anadditive in a lubricant. The amount of the alkylphenol detergent in atransmission lubricant may be 0.01 to 2 percent by weight, on anoil-free basis, but including the calcium carbonate and other saltspresent in an overbased composition, or from about 0.1 to about 1.75 wt%, or about 0.2 to about 1.5.

A lubricant composition may contain alkylphenol-containing detergentsdifferent from that of the disclosed technology in an amount of fromabout 0.1 to 1.5 weight percent, or 0.2 to 1.25, or 0.3 to 1 weightpercent, and is free of or substantially free of analkylphenol-containing detergent derived from alkylphenol which isderived from oligomers of propylene, especially tetrapropenyl.“Substantially free of” in this case means no more than 0.01 weightpercent or an amount considered to arise through contamination or otherunintentional means.

Oil of Lubricating Viscosity

The lubricating composition comprises an oil of lubricating viscosity.Such oils include natural and synthetic oils, oil derived fromhydrocracking, hydrogenation, and hydrofinishing, unrefined, refined,re-refined oils or mixtures thereof. A more detailed description ofunrefined, refined and re-refined oils is provided in InternationalPublication WO2008/147704, paragraphs [0054] to [0056] (a similardisclosure is provided in US Patent Application 2010/197536, see [0072]to [0073]). A more detailed description of natural and syntheticlubricating oils is described in paragraphs [0058] to [0059]respectively of W02008/147704 (a similar disclosure is provided in USPatent Application 2010/197536, see [0075] to [0076]). Synthetic oilsmay also be produced by Fischer-Tropsch reactions and typically may behydroisomerized Fischer-Tropsch hydrocarbons or waxes. In one embodimentoils may be prepared by a Fischer-Tropsch gas-to-liquid syntheticprocedure as well as other gas-to-liquid oils.

Oils of lubricating viscosity may also be defined as specified in April2008 version of “Appendix E—API Base Oil Interchangeability Guidelinesfor Passenger Car Motor Oils and Diesel Engine Oils”, section 1.3Sub-heading 1.3. “Base Stock Categories”. The API Guidelines are alsosummarized in US Patent U.S. Pat. No. 7,285,516 (see column 11, line 64to column 12, line 10).

In one embodiment the oil of lubricating viscosity may be an API Group Ito III mineral oil, a Group IV synthetic oil, or a Group V naphthenic orester synthetic oil, or mixtures thereof. In one embodiment the oil oflubricating viscosity may be an API Group II, Group III mineral oil, ora Group IV synthetic oil, or mixtures thereof. Group II+ refers to GroupII base oils, to a generally recognized (but not officially identifiedby the API) as having a Viscosity Index of 110-119 and lower volatilitythan other Group II oils. Additionally, the oil of lubricating viscositymay be a Group III+ base oil, a term which refers to a Group III baseoil having a Viscosity Index greater than or equal to 130. Group III+base oils are generally known in the art and are described in an articlepublished in ‘Lube Report’ (see “SK Sees Group III Short-fall”, by NancyDeMarco. The article may be obtained fromhttp://www.aselube.com/media/11910/sk_sees_group_iii_shortfall.pdf

The amount of the oil of lubricating viscosity present is typically thebalance remaining after subtracting from 100 weight % the sum of theamount of the additives of the disclosed technology and the otherperformance additives.

The lubricating composition may be in the form of a concentrate and/or afully formulated lubricant. If the lubricating composition of thedisclosed technology (comprising the additives disclosed herein) is inthe form of a concentrate which may be combined with additional oil toform, in whole or in part, a finished lubricant), the ratio of the ofthese additives to the oil of lubricating viscosity and/or to diluentoil include the ranges of 1:99 to 99:1 by weight, or 80:20 to 10:90 byweight. Typically the lubricating composition of the disclosedtechnology comprises at least 50 weight %, or at least 60 weight %, orat least 70 weight %, or at least 80 weight % of an oil of lubricatingviscosity.

Other Performance Additives

A lubricant composition may be prepared by adding the alkylphenoldetergent described herein above to an oil of lubricating viscosity,optionally in the presence of other performance additives (as describedherein below).

The lubricant composition may further include other additives. In oneembodiment the invention provides a lubricant composition furthercomprising at least one of a dispersant, an antiwear agent, a dispersantviscosity modifier, a friction modifier, a viscosity modifier, anantioxidant, an overbased detergent (other than the alkylphenoldetergent described above), a foam inhibitor, a demulsifier, a pourpoint depressant or mixtures thereof. In one embodiment the inventionprovides a lubricant composition further comprising at least one of apolyisobutylene succinimide dispersant, an antiwear agent, a corrosioninhibitor, a dispersant viscosity modifier, a friction modifier, aviscosity modifier (typically a polymethacrylate having linear, comb orstar architecture), an antioxidant (including phenolic and aminicantioxidants), an overbased detergent (including overbased sulphonates,phenates, and salicylates other than the alkylphenol detergent describedabove), or mixtures thereof.

The amount of each other performance additive and chemistry of the otherperformance additive will depend on type of driveline device beinglubricated. When present common additives across each drivelinelubricant includes viscosity modifiers, dispersants, foam inhibitors,corrosion inhibitors, pour point depressants, demulsifiers, and sealswell agents.

Viscosity modifiers may be included in the lubricant composition.Viscosity modifiers are usually polymers, including polyisobutenes,polymethacrylic acid esters, diene polymers, polyalkylstyrenes,esterified styrene-maleic anhydride copolymers, alkenylarene-conjugateddiene copolymers, and polyolefins. Multifunctional viscosity improvers,which also have dispersant and/or antioxidancy properties are known andmay optionally be used. The amount of viscosity modifier may range from0.1 to 70 wt %, or 1 to 50 wt %, or 2 to 40 wt %. Typically theviscosity modifier may be a polymethacrylate, or mixtures thereof.

The lubricant may comprise a dispersant, which may be anitrogen-containing dispersants, for example a hydrocarbyl substitutednitrogen containing additive. Suitable hydrocarbyl substituted nitrogencontaining additives include ashless dispersants and polymericdispersants. Ashless dispersants are so-named because, as supplied, theydo not contain metal and thus do not normally contribute to sulfated ashwhen added to a lubricant. However they may, of course, interact withambient metals once they are added to a lubricant which includesmetal-containing species. Ashless dispersants are characterized by apolar group attached to a relatively high molecular weight hydrocarbonchain. Examples of such materials include succinimide dispersants,Mannich dispersants.

The dispersant may be post-treated with other reagents, or notpost-treated. The dispersant may be post-treated with urea, thiourea,dimercaptothiadiazoles, carbon disulphide, aldehydes, ketones,carboxylic acids, hydrocarbon-substituted succinic anhydrides, maleicanhydride, nitriles, epoxides, and phosphorus compounds. Typically asuccinimide dispersant may optionally be post-treated by conventionalmethods by a reaction with any of a variety of other agents.

The polyamine may be an alkylenepolyamine. The alkylenepolyamine mayinclude an ethylenepolyamine, a propylenepolyamine, a butylenepolyamine,or mixtures thereof. Examples of propylenepolyamine includepropylenediamine, dipropylenetriamine and mixtures thereof.

In one embodiment the polyamine is chosen from ethylenediamine,diethylenetriamine, triethylenetetramine, tetraethylenepentamine,pentaethylenehexamine, polyamine still bottoms and mixtures thereof.

In another embodiment, the lubricating composition may have an antiwearadditive comprising a phosphate amine salt. The C₂₋C₁₈ (or C₂ to C₈ orC₁₆₋C₁₈) di- or tri-hydrocarbyl phosphite, or mixtures thereof may berepresented by the formula:

wherein at least one of R^(6,) R⁷ and R⁸ may be a hydrocarbyl groupcontaining at least 4 carbon atoms and the other may be hydrogen or ahydrocarbyl group. In one embodiment R^(6,) R⁷ and R⁸ are allhydrocarbyl groups. The hydrocarbyl groups may be alkyl, cycloalkyl,aryl, acyclic or mixtures thereof. In the formula with all three groupsR^(6,) R⁷ and R^(8,) the compound may be a tri-hydrocarbyl substitutedphosphite i.e., R^(6,) R⁷ and R⁸ are all hydrocarbyl groups and in someembodiments may be alkyl groups. Typically the di- or tri-hydrocarbylphosphite comprises dibutyl phosphite or oleyl phosphite.

Foam inhibitors that may be useful in the compositions includepolysiloxanes, copolymers of ethyl acrylate and 2-ethylhexylacrylate andoptionally vinyl acetate; demulsifiers including fluorinatedpolysiloxanes, trialkyl phosphates, polyethylene glycols, polyethyleneoxides, polypropylene oxides and (ethylene oxide-propylene oxide)polymers.

Pour point depressants that may be useful in the compositions includepolyalphaolefins, esters of maleic anhydride-styrene copolymers,poly(meth)acrylates, polyacrylates or polyacrylamides.

Demulsifiers include trialkyl phosphates, and various polymers andcopolymers of ethylene glycol, ethylene oxide, propylene oxide, ormixtures thereof.

Seal swell agents include sulpholene derivatives Exxon Necton-37™ (FN1380) and Exxon Mineral Seal Oil™ (FN 3200).

Manual Transmission Lubricant

In one embodiment the invention provides a lubricant compositioncomprising:

-   -   an oil of lubricating viscosity,    -   a thiadiazole (typically present at 0.05 to 1 wt %, or 0.07 to        0.7 wt %, or 0.1 to 0.3 wt %, or 0.15 to 0.25 wt %),    -   a dispersant (typically present at 0.1 to 5 wt %, or 0.3 to 4 wt        %, or 1 to 3 wt %, or 0.1 to 3 wt %),    -   a phosphorus-containing antiwear agent chosen from (i) a        non-ionic phosphorus compound, which may be a hydrocarbyl        phosphite; or (ii) an amine salt of a phosphorus compound,    -   from about 0.1 to about 2 wt % of a detergent, typically present        in an amount to deliver 110 to 700ppm, 130 to 600ppm, 150 to        500ppm or 160 to 400ppm calcium; and wherein from about 0.01 to        about 2 wt %, or from about 0.1 to about 1.75 wt %, or about 0.2        to about 1.5 wt % of the detergent comprises alkylphenol        detergent described herein.

The manual transmission may have synchromesh, or in another embodimentthe manual transmission does not have a synchromesh. The synchromesh maybe composed of aluminum, steel, bronze, molybdenum, brass (sintered ornon-sintered), carbon in the form of fibers, graphitic material(optionally in combination with a cellulosic material), or a cellulosicmaterial, or a phenolic resin.

[0073]In one embodiment the lubricant may comprise 0.03 to 1.0 wt %, or0.1 to 0.6 wt %, or 0.2 to 0.5 wt % of calcium.

[0074]The detergent may be calcium or magnesium based, and the detergentmay have at least 200 TBN, or 250 to 1000, or 450 to 900 or 650 to 800mg KOH/g on an oil free basis. Typically the detergent is a calciumbased detergent.

[0075]The lubricant may have 100 to 2000 ppm, 150 to 1500 ppm, 200 to1000, or 250 to 800 ppm, or 500 to 875 ppm of phosphorus delivered by anantiwear agent i.e., delivered by zinc dialkyl dithiophosphate oranother phosphorus-containing antiwear agent.

In one embodiment the invention provides a method of lubricating amanual transmission comprising supplying to the manual transmission alubricant composition comprising:

-   -   an oil of lubricating viscosity,    -   a thiadiazole (typically present at 0.05 to 1 wt %, or 0.07 to        0.7 wt %, or 0.1 to 0.3 wt %, or 0.15 to 0.25 wt %),    -   a dispersant (typically present at 0.1 to 5 wt %, or 0.3 to 4 wt        %, or 1 to 3 wt %, or 0.1 to 3 wt %),    -   a phosphorus-containing antiwear agent chosen from (i) a        non-ionic phosphorus compound, which may be a hydrocarbyl        phosphite; or (ii) an amine salt of a phosphorus compound,    -   from about 0.1 to about 5 wt % of a detergent, typically present        in an amount to deliver 110 to 700 ppm, 130 to 600 ppm, 150 to        500 ppm or 160 to 400 ppm calcium; and wherein from about 0.01        to about 2 wt %, or from about 0.1 to about 1.75 wt %, or about        0.2 to about 1.5 wt % of the detergent comprises alkylphenol        detergent described herein.

The thiadiazole compound may include mono- or di-hydrocarbyl substituted2,5-dimercapto-1,3,4-thiadiazole compounds. Examples of a thiadiazoleinclude 2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof, ahydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole, ahydrocarbylthio-substituted 2,5-dimercapto-1,3,4-thiadiazole, oroligomers thereof. The oligomers of hydrocarbyl-substituted2,5-dimercapto-1,3,4-thiadiazole typically form by forming asulphur-sulphur bond between 2,5-dimercapto-1,3,4-thiadiazole units toform oligomers of two or more of said thiadiazole units. Thesethiadiazole compounds may also be used in the post treatment ofdispersants as mentioned below in the formation of adimercaptothiadiazole derivative of a polyisobutylene succinimide.

Examples of a suitable thiadiazole compound include at least one of adimercaptothiadiazole, 2,5-dimercapto-[1,3,4]-thiadiazole,3,5-dimercapto-[1,2,4]-thiadiazole, 3,4-dimercapto-[1,2,5]-thiadiazole,or 4-5-dimercapto-[1,2,3]-thiadiazole. Typically readily availablematerials such as 2,5-dimercapto-1,3,4-thiadiazole or ahydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole or ahydrocarbylthio-substituted 2,5-dimercapto-1,3,4-thiadiazole arecommonly utilised.

The lubricant may contain a detergent aside from the aklylphenoldetergent described above. The detergent may be neutral or overbased,typically overbased. The detergent may be calcium or magnesiumcontaining, typically calcium containing.

Another component of the disclosed lubricant can be an overbased,carbonated calcium or magnesium arylsulphonate detergent having a totalbase number (TBN) of at least 640 as calculated on an oil-free basis, ora mixture of such detergents. Detergents in general are typicallyoverbased materials, otherwise referred to as overbased or superbasedsalts, which are generally homogeneous Newtonian systems having by ametal content in excess of that which would be present forneutralization according to the stoichiometry of the metal and thedetergent anion. The amount of excess metal is commonly expressed interms of metal ratio, that is, the ratio of the total equivalents of themetal to the equivalents of the acidic organic compound. Overbasedmaterials are prepared by reacting an acidic material (such as carbondioxide) with an acidic organic compound, an inert reaction medium(e.g., mineral oil), a stoichiometric excess of a metal base, and apromoter such as a phenol or alcohol. The acidic organic material willnormally have a sufficient number of carbon atoms, to provideoil-solubility.

Overbased detergents may be characterized by Total Base Number (TBN),the amount of strong acid needed to neutralize all of the material'sbasicity, expressed as mg KOH per gram of sample. TBN is a verywell-known parameter that is described in ASTM D 4739. Since overbaseddetergents are commonly provided in a form which contains diluent oil,for the purpose of this document, TBN is to be recalculated to anoil-free basis. Various detergents may have a TBN of 100 to 1000, or 150to 800, or, 400 to 700. The detergents may have a TBN of at least 640,for instance, 650 to 1000, or even 680 to 800. In each case, the unitsare mg KOH/g.

Typically the detergent is an overbased calcium sulphonate detergent,but other metals may also be present, whether in a sulphonate detergent(for example, an overbased magnesium arylsulphonate detergent) or adifferent detergent substrate (for example, an overbased calcium phenatedetergent). The metal compounds generally useful in making the basicmetal salts are generally any Group 1 or Group 2 metal compounds (CASversion of the Periodic Table of the Elements). Examples include alkalimetals such as sodium, potassium, lithium, copper, magnesium, calcium,barium, zinc, and cadmium. In one embodiment the metals are sodium,magnesium, or calcium. The anionic portion of the salt may be hydroxide,oxide, carbonate, borate, or nitrate. The detergents may be calcium ormagnesium detergents, typically prepared using calcium or magnesiumoxide or calcium or magnesium hydroxide. Since the detergents ofparticular interest are carbonated detergents, they will be materialsthat have been treated with carbon dioxide. Such treatment leads to moreefficient incorporation of basic metal into the composition. Formationof high TBN detergents involving reaction with carbon dioxide isdisclosed, for instance, in U.S. Pat. No. 7,238,651, Kocsis et al., Jul.3, 2007, see, for instance, examples 10-13 and the claims. Otherdetergents, however, may also optionally be present, which need not becarbonated or need not be so highly overbased (i.e., of lower TBN).However, if multiple detergents are present, it is desirable that theoverbased calcium or magnesium arylsulphonate detergent is present asthe predominant amount by weight of the metal detergents, that is, atleast 50 weight percent or at least 60 or 70 or 80 or 90 weight percentof the metal-containing detergents, on an oil free basis.

The lubricants may contain an overbased sulphonate detergent. Suitablesulphonic acids include sulphonic and thiosulphonic acids, includingmono- or poly-nuclear aromatic or cycloaliphatic compounds. Certainoil-soluble sulphonates may be represented by R²-T-(SO₃ ⁻)_(a) orR³—(SO₃ ⁻)_(b), where a and b are each at least one; T is a cyclicnucleus such as benzene or toluene; R² is an aliphatic group such asalkyl, alkenyl, alkoxy, or alkoxyalkyl; (R²)-T typically contains atotal of at least 15 carbon atoms; and R³ is an aliphatic hydrocarbylgroup typically containing at least 15 carbon atoms. The groups T,R^(2,) and R³ may also contain other inorganic or organic substituents;they may also be described as hydrocarbyl groups. In one embodiment thesulphonate detergent may be a predominantly linearalkylbenzenesulphonate detergent as described in paragraphs [0026] to[0037] of US Patent Application 2005-065045. In some embodiments thelinear alkyl (or hydrocarbyl) group may be attached to the benzene ringanywhere along the linear chain of the alkyl group, but often in the 2,3, or 4 position of the linear chain, and in some instancespredominantly in the 2 position. In other embodiments, the alkyl (orhydrocarbyl) group may be branched, that is, formed from a branchedolefin such as propylene or 1-butene or isobutene. Sulphonate detergentshaving a mixture of linear and branched alkyl groups may also be used.

In certain embodiments the carbonated calcium or magnesiumarylsulphonate detergent may be based on an alkylated and sulphonatedbenzene; in another embodiment, it may be based on an alkylated andsulphonated toluene. In either case there may be one or two or three,and in certain embodiments one, alkyl (or hydrocarbyl) group attached tothe aromatic ring, in addition to the methyl group if toluene is used asthe starting aromatic compound. In one embodiment, the detergent is amonoalkylbenzenemonosulphonate, and in another embodiment it is amonoalkyltoluenemonosulphonate. If there is one alkyl group, it maycontain a sufficient number of carbon atoms to impart oil-solubility tothe detergent, such as at least 8 carbon atoms, or 10 to 100 carbonatoms, or 10 to 50 carbon atoms, or 12 to 36 carbon atoms, or 14 to 24or 16 to 20 or alternatively about 18 carbon atoms. If more than onealkyl group (other than methyl) is present, each alkyl group may havethe afore-described number of carbon atoms, or all the alkyl groupstogether may have in total the afore-described number of carbon atoms,(e.g., two C12 alkyl groups for a total of 24 carbon atoms in the alkylgroups). Another type of overbased material that may additionally bepresent (that is, in addition to the alkylphenol detergent describedabove) in certain embodiments of the present invention is an overbasedphenate detergent. Certain commercial grades of calcium or magnesiumsulphonate detergents contain minor amounts of calcium or magnesiumphenate detergents to aid in their processing or for other reasons andmay contain, for instance, 4% phenate substrate content and 96%sulphonate substrate content. The phenols useful in making phenatedetergents may be represented by (R¹)_(a)—Ar—(OH)_(b), where R¹ is analiphatic hydrocarbyl group of 4 to 400 or 6 to 80 or 6 to 30 or 8 to 25or 8 to 15 carbon atoms; Ar is an aromatic group such as benzene,toluene or naphthalene; a and b are each at least one, the sum of a andb being up to the number of displaceable hydrogens on the aromaticnucleus of Ar, such as 1 to 4 or 1 to 2. There is typically an averageof at least 7 or 8 aliphatic carbon atoms provided by the R¹ groups foreach phenol compound, and in some instances about 12 carbon atoms.Phenate detergents are also sometimes provided as sulphur-bridgedspecies or as methylene-bridged species. Sulphur-bridged species may beprepared by reacting a hydrocarbyl phenol with sulphur.Methylene-bridged species may be prepared by reacting a hydrocarbylphenol with formaldehyde (or a reactive equivalent such asparaformaldehyde). Examples include sulphur-bridged dodecylphenol(overbased Ca salt) and methylene-coupled heptylphenol.

In another embodiment, an optional, additional overbased material is anoverbased saligenin detergent. Overbased saligenin detergents arecommonly overbased magnesium salts which are based on saligeninderivatives. A general example of such a saligenin derivative may berepresented by the formula:

where X is —CHO or —CH₂OH, Y is —CH₂— or —CH₂OCH₂—, and the —CHO groupstypically comprise at least 10 mole percent of the X and Y groups; M ishydrogen, ammonium, or a valence of a metal ion (that is, if M ismultivalent, one of the valences is satisfied by the illustratedstructure and other valences are satisfied by other species such asanions or by another instance of the same structure), R₁ is ahydrocarbyl group of 1 to 60 carbon atoms, m is 0 to typically 10, andeach p is independently 0, 1, 2, or 3, provided that at least onearomatic ring contains an R¹ substituent and that the total number ofcarbon atoms in all R¹ groups is at least 7. When m is 1 or greater, oneof the X groups may be hydrogen. In one embodiment, M is a valence (orequivalent) of a Mg ion or a mixture of Mg and hydrogen. Saligenindetergents are disclosed in greater detail in U.S. Pat. No. 6,310,009,with special reference to their methods of synthesis (Column 8 andExample 1) and preferred amounts of the various species of X and Y(Column 6).

Other optional detergents include salixarate detergents. Salixaratedetergents are overbased materials that may be represented by a compoundcomprising at least one unit of formula (I) or formula (II):

each end of the compound having a terminal group of formula (III) or(IV):

such groups being linked by divalent bridging groups A, which may be thesame or different. In formulas (I)-(IV) R³ is hydrogen, a hydrocarbylgroup, or a valence of a metal ion; R² is hydroxyl or a hydrocarbylgroup, and j is 0, 1, or 2; R⁶ is hydrogen, a hydrocarbyl group, or ahetero-substituted hydrocarbyl group; either R⁴ is hydroxyl and R⁵ andR⁷ are independently either hydrogen, a hydrocarbyl group, orhetero-substituted hydrocarbyl group, or else R⁵ and R⁷ are bothhydroxyl and R⁴ is hydrogen, a hydrocarbyl group, or ahetero-substituted hydrocarbyl group; provided that at least one ofR^(4,) R^(5,) R⁶ and R⁷ is hydrocarbyl containing at least 8 carbonatoms; and wherein the molecules on average contain at least one of unit(I) or (III) and at least one of unit (II) or (IV) and the ratio of thetotal number of units (I) and (III) to the total number of units of (II)and (IV) in the composition is 0.1:1 to 2:1. The divalent bridging group“A,” which may be the same or different in each occurrence, includes—CH₂— and —CH₂OCH₂—, either of which may be derived from formaldehyde ora formaldehyde equivalent (e.g., paraform, formalin).

Salixarate derivatives and methods of their preparation are described ingreater detail in U.S. Pat. No. 6,200,936 and PCT Publication WO01/56968. It is believed that the salixarate derivatives have apredominantly linear, rather than macrocyclic, structure, although bothstructures are intended to be encompassed by the term “salixarate.” Inone embodiment, a salixarate detergent may contain a portion ofmolecules represented (prior to neutralization) by the structure:

where the R⁸ groups are independently hydrocarbyl groups containing atleast 8 carbon atoms.

Glyoxylate detergents are also optional overbased materials. They arebased on an anionic group which, in one embodiment, may have thestructure:

wherein each R is independently an alkyl group containing at least 4 or8 carbon atoms, provided that the total number of carbon atoms in allsuch R groups is at least 12 or 16or 24. Alternatively, each R may be anolefin polymer substituent. The acidic material upon from which theoverbased glyoxylate detergent is prepared is the condensation productof a hydroxyaromatic material such as a hydrocarbyl-substituted phenolwith a carboxylic reactant such as glyoxylic acid or anotheromega-oxoalkanoic acid. Overbased glyoxylic detergents and their methodsof preparation are disclosed in greater detail in U.S. Pat. No.6,310,011 and references cited therein.

Another optional overbased detergent is an overbased salicylate, e,g.,an alkali metal or alkaline earth metal salt of a substituted salicylicacid. The salicylic acids may be hydrocarbyl-substituted wherein eachsubstituent contains an average of at least 8 carbon atoms persubstituent and 1 to 3 substituents per molecule. The substituents maybe polyalkene substituents. In one embodiment, the hydrocarbylsubstituent group contains 7 to 300 carbon atoms and may be an alkylgroup having a molecular weight of 150 to 2000. Overbased salicylatedetergents and their methods of preparation are disclosed in U.S. Pat.Nos. 4,719,023 and 3,372,116.

Other optional overbased detergents may include overbased detergentshaving a Mannich base structure, as disclosed in U.S. Pat. No.6,569,818.

In certain embodiments, the hydrocarbyl substituents onhydroxy-substituted aromatic rings in the above detergents (e.g.,phenate, saligenin, salixarate, glyoxylate, or salicylate) are free ofor substantially free of C₁₂ aliphatic hydrocarbyl groups (e.g., lessthan 1%, 0.1%, or 0.01% by weight of the substituents are C₁₂ aliphatichydrocarbyl groups). In some embodiments such hydrocarbyl substituentscontain at least 14 or at least 18 carbon atoms.

Optionally the lubricant may further include an additional phosphoruscontaining material and may include a metal salt of a phosphorus acid.Metal salts may have the formula:

[(R⁸O)(R⁹O)P(═S)—S]_(n)-M

where R⁸ and R⁹ are independently hydrocarbyl groups containing 3 to 30carbon atoms, are readily obtainable by heating phosphorus pentasulfide(P₂S₅) and an alcohol or phenol to form an 0,0-dihydrocarbylphosphorodithioic acid. The alcohol which reacts to provide the R⁸ andR⁹ groups may be a mixture of alcohols, for instance, a mixture ofisopropanol and 4-methyl-2-pentanol, and in some embodiments a mixtureof a secondary alcohol and a primary alcohol, such as isopropanol and2-ethylhexanol. The resulting acid may be reacted with a basic metalcompound to form the salt. The metal M, having a valence n, generally isaluminum, tin, manganese, cobalt, nickel, zinc, or copper, and in manycases, zinc, to form zinc dialkyldithiophosphates. Such materials arewell known and readily available to those skilled in the art oflubricant formulation. Suitable variations to provide low phosphorusvolatility are disclosed, for instance, in US published application2008-0015129, see, e.g., claims.

Mixtures of amines may also be used in the invention. In one embodimenta useful mixture of amines is “Primene® 81R” and “Primene® JMT.”Primene® 81R and Primene® JMT (both produced and sold by Rohm & Haas)are mixtures of C11 to C14 tertiary alkyl primary amines and C18 to C22tertiary alkyl primary amines respectively.

In one embodiment the hydrocarbyl amine salt of an alkylphosphoric acidester is the reaction product of a C14 to C18 alkylated phosphoric acidwith Primene 81R™ (produced and sold by Rohm & Haas) which is a mixtureof C11 to C14 tertiary alkyl primary amines.

Examples of hydrocarbyl amine salts of dialkyldithiophosphoric acidesters include the reaction product(s) of isopropyl, methyl-amyl(4-methyl-2-pentyl or mixtures thereof), 2-ethylhexyl, heptyl, octyl ornonyl dithiophosphoric acids with ethylene diamine, morpholine, orPrimene 81R™, and mixtures thereof.

In one embodiment the dithiophosphoric acid may be reacted with anepoxide or a glycol. This reaction product is further reacted with aphosphorus acid, anhydride, or lower ester. The epoxide includes analiphatic epoxide or a styrene oxide. Examples of useful epoxidesinclude ethylene oxide, propylene oxide, butene oxide, octene oxide,dodecene oxide, styrene oxide and the like. In one embodiment theepoxide is Propylene oxide. The glycols may be aliphatic glycols havingfrom 1 to about 12, or from about 2 to about 6, or about 2 to about 3carbon atoms. The dithiophosphoric acids, glycols, epoxides, inorganicphosphorus reagents and methods of reacting the same are described inU.S. Pat. Nos. 3,197,405 and 3,544,465. The resulting acids may then besalted with amines. An example of suitable dithiophosphoric acid isprepared by adding phosphorus pentoxide (about 64 grams) at about 58° C.over a period of about 45 minutes to about 514 grams of hydroxypropylO,O-di(4-methyl-2-pentyl)phosphorodithioate (prepared by reactingdi(4-methyl-2-pentyl)-phosphorodithioic acid with about 1.3 moles ofpropylene oxide at about 25° C. ). The mixture is heated at about 75° C.for about 2.5 hours, mixed with a diatomaceous earth and filtered atabout 70° C. The filtrate contains about 11.8% by weight phosphorus,about 15.2% by weight sulfur, and an acid number of 87 (bromophenolblue).

If the additional phosphorus containing material is present it mayprovide 1 % to 90 %, or 10 to 80 %, or 20 to 70 % of the total amount ofphosphorus to the lubricant. In one embodiment the additional phosphoruscontaining material is present, and in one embodiment the additionalphosphorus containing material is present is absent.

The lubricant may further include an antioxidant, or mixtures thereof.The Antioxidant may include molybdenum compounds such as molybdenumdithiocarbamates, sulphurised olefins, hindered phenols, aminiccompounds such as alkylated diphenylamines (typically di-nonyldiphenylamine, octyl diphenylamine, or di-octyl diphenylamine). Whenpresent, the antioxidant may be present at 0 to 3 wt %, or 0.1 to 2.5 wt%, or 0.2 to 1.5 wt %.

Automatic Transmission Lubricants

In one embodiment the invention provides a lubricant compositioncomprising:

-   -   an oil of lubricating viscosity,    -   a dispersant typically present at 0.01 to 5 wt %, or 0.05 to 3        wt %, or 0.1 to 3 wt %, or or 0.1 to 2 wt %,    -   from about 0.1 to about 1, typically present in an amount to        deliver 40 to 1000 ppm, 50 to 700 ppm, 60 to 600 ppm or 70 to        250 ppm calcium; and wherein from about 0.01 to about 0.8 wt %,        or from about 0.1 to about 0.5 wt %, or about 0.2 to about 0.15        wt % of the detergent comprises alkylphenol detergent described        herein, and    -   a friction modifier typically present at 0 to 4 wt %, or 0.1 to        4 wt %, 0.2 to 3 wt %, 0.3 to 3 wt %, 0.25 to 2.5 wt %. In one        embodiment the friction modifier is present, and in an        alternative embodiment the friction modifier is not present.

In one embodiment the invention provides a method of lubricating anautomatic transmission comprising supplying to the automatictransmission a lubricant composition comprising:

-   -   an oil of lubricating viscosity,    -   a dispersant typically present at 0.5 to 3 wt %, or 1 to 2.5 wt        %, or 1.5 to 4 wt %, or 1.5 to 3 wt %,    -   a phosphorus-containing antiwear agent chosen from (i) a        non-ionic phosphorus compound, which may be a hydrocarbyl        phosphite; or (ii) an amine salt of a phosphorus compound,    -   a thiadiazole, typically present at 0.1 to 0.5 wt %,or 0.2 to        0.4 wt %, or 0.25 to 0.35 wt %.    -   from about 0.1 to about 5 wt % of a detergent, typically present        in an amount to deliver 40 to 700 ppm, 50 to 600 ppm, 60 to 500        ppm or 70 to 250 ppm calcium; and wherein from about 0.01 to        about 2 wt %, or from about 0.1 to about 1.75 wt %, or about 0.2        to about 1.5 wt % of the detergent comprises alkylphenol        detergent described herein, and    -   a friction modifier typically present at 0 to 4 wt %, or 0.1 to        4 wt %, 0.2 to 3 wt %, 0.3 to 3 wt %, 0.25 to 2.5 wt %. In one        embodiment the friction modifier is present, and in an        alternative embodiment the friction modifier is not present.

The automatic transmission includes continuously variable transmissions(CVT), infinitely variable transmissions (IVT), Toroidal transmissions,continuously slipping torque converted clutches (CSTCC), steppedautomatic transmissions or dual clutch transmissions (DCT).

The calcium-containing detergent may be an overbased detergent, anon-overbased detergent, or mixtures thereof. Typically the detergentmay be overbased.

The preparation of the calcium-containing detergent is known in the art.Patents describing the preparation of overbased calcium-containingdetergents include U.S. Pat. Nos. 2,501,731; 2,616,905; 2,616,911;2,616,925; 2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162;3,318,809; 3,488,284; and 3,629,109.

As used herein the TBN values quoted and associated range of TBN is on“an as is basis,” i.e., containing conventional amounts of diluent oil.Conventional amounts of diluent oil typically range from 30 wt % to 60wt % (often 40 wt % to 55 wt %) of the detergent component.

A more detailed description of the expressions “metal ratio”, TBN and“soap content” are known to a person skilled in the art and explained instandard textbook entitled “Chemistry and Technology of Lubricants”,Third Edition, Edited by R. M. Mortier and S. T. Orszulik, Copyright2010, pages 219 to 220 under the sub-heading 7.2.5. DetergentClassification.

The calcium-containing detergent may be a non-overbased detergent (mayalso be referred to as a neutral detergent). The TBN of a non-overbasedmay be 20 to less than 200, or 30 to 100, or 35 to 50 mg KOH/g. The TBNof a non-overbased calcium-containing detergent may also be 20 to 175,or 30 to 100 mg KOH/g. When a non-overbased calcium-containing detergentis prepared from a strong acid such as a hydrocarbyl-substitutedsulphonic acid, the TBN may be lower (for example 0 to 50 mg KOH/g, or10 to 20 mg KOH/g).

The calcium-containing detergent may be an overbased detergent, whichmay have a TBN of greater than 200 mg KOH/g (typically 250 to 600, or300 to 500 mg KOH/g).

The calcium-containing detergent may be formed by the reaction of abasic calcium compound and an acidic detergent substrate. The acidicdetergent substrate may include an alkyl phenol, an aldehyde-coupledalkyl phenol, a sulphurised alkyl phenol, an alkyl aromatic sulphonicacid (such as, alkyl naphthalene sulphonic acid, alkyl toluene sulphonicacid or alkyl benzene sulphonic acid), an aliphatic carboxylic acid, acalixarene, a salixarene, an alkyl salicylic acid, or mixtures thereof.

The metal basic compound is used to supply basicity to the detergent.The basic calcium compound is a compound of a hydroxide or oxide of themetal.

The oxides and/or hydroxides may be used alone or in combination. Theoxides or hydroxides may be hydrated or dehydrated, although hydrated istypical. In one embodiment the basic calcium compound may be calciumhydroxide, which may be used alone or mixtures thereof with other metalbasic compounds. Calcium hydroxide is often referred to as lime. In oneembodiment the metal basic compound may be calcium oxide which may beused alone or mixtures thereof with other metal basic compounds.

Collectively, when the alkyl phenol, the aldehyde-coupled alkyl phenol,and the sulphurised alkyl phenol are used to prepare acalcium-containing detergent, the detergent may be referred to as acalcium phenate. The calcium phenate may be an alkyl phenate, analdehyde-coupled alkyl phenate, a sulphurised alkyl phenate, or mixturesthereof.

The TBN of a calcium phenate may vary from less 200, or 30 to 175typically 150 to 175) mg KOH/g for a neutral phenate to 200 or more to500, or210 to 400 (typically 230 to 270) mg KOH/g for an overbasedphenate.

The alkyl group of a phenate (i.e., an alkyl phenate) may contain 4 to80, or 6 to 45, or 8 to 20, or 9 to 15 carbon atoms.

In one embodiment the calcium-containing detergent may be a sulphonate,or mixtures thereof. The sulphonate may be prepared from a mono- ordi-hydrocarbyl-substituted benzene (or naphthalene, indenyl, indanyl, orbicyclopentadienyl) sulphonic acid, wherein the hydrocarbyl group maycontain 6 to 40, or 8 to 35 or 9 to 30 carbon atoms.

The hydrocarbyl group may be derived from polypropylene or a linear orbranched alkyl group containing at least 10 carbon atoms. Examples of asuitable alkyl group include branched and/or linear decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,octadecyl, octadecenyl, nonodecyl, eicosyl, un-eicosyl, do-eicosyl,tri-eicosyl, tetra-eicosyl, penta-eicosyl, hexa-eicosyl or mixturesthereof.

In one embodiment the hydrocarbyl-substituted sulphonic acid may includepolypropene benzenesulphonic acid and/or C₁₆₋C₂₄ alkyl benzenesulphonicacid, or mixtures thereof.

In one embodiment a calcium sulphonate detergent may be a predominantlylinear alkylbenzene sulphonate detergent having a metal ratio of atleast 8 as is described in paragraphs [0026] to [0037] of US PatentApplication 2005065045 (and granted as U.S. Pat. No. 7,407,919). In someembodiments the linear alkyl group may be attached to the benzene ringanywhere along the linear chain of the alkyl group, but often in the 2,3 or 4 position of the linear chain, and in some instances predominantlyin the 2 position.

When neutral or slightly basic, a calcium sulphonate detergent may haveTBN of less than 100, or less than 75, typically 20 to 50 mg KOH/g, or 0to 20 mg KOH/g.

When overbased, a calcium sulphonate detergent may have a TBN greaterthan 200, or 300 to 550, or 350 to 450 mg KOH/g.

The detergent may be borated or non-borated.

Chemical structures for sulphonates, and phenates detergents are knownto a person skilled in the art. The standard textbook entitled“Chemistry and Technology of Lubricants”, Third Edition, Edited by R. M.Mortier and S. T. Orszulik, Copyright 2010, pages 220 to 223 under thesub-heading 7.2.6 provide general disclosures of said detergents andtheir structures.

In one embodiment the calcium-containing detergent may be an overbasedcalcium sulphonate, an overbased calcium phenate, or mixtures thereof.Typically the detergent may be an overbased calcium sulphonate.

In one embodiment the calcium-containing detergent may be in a mixturewith a having zinc-, barium-, sodium-, or magnesium-containingdetergent. The zinc-, barium-, sodium-, or magnesium-containingdetergent is also well known in the art and described in the samereferences describing a calcium-containing detergent. The TBN and metalratios may however, differ slightly. The zinc-, barium-, sodium-, ormagnesium-containing detergent may be a phenate, a sulphur-containingphenate, sulphonate, salixarate or salicylate. Typically a zinc-,barium-, sodium-, or magnesium-containing detergent may be a magnesiumphenate, a magnesium sulphur-containing phenate, or a magnesiumsulphonate.

The dispersant is described above.

The lubricant composition may include a friction modifier, typically atleast two friction modifiers. Useful friction modifiers are describedbelow.

In one embodiment the friction modifier may be formed by thecondensation of the hydroxyalkyl compound with an acylating agent or anamine. A more detailed description of the hydroxyalkyl compound isdescribed in U.S. Patent Application 60/725360 (filed on Oct. 11, 2005,inventors Bartley, Lahiri, Baker and Tipton) in paragraphs 8, 19-21. Thefriction modifier disclosed in U.S. Patent Application 60/725360 may bean amide represented by the formula R¹R²N—C(O)R³, wherein R¹ and R² areeach independently hydrocarbyl groups of at least 6 carbon atoms and R³is a hydroxyalkyl group of 1 to 6 carbon atoms or a group formed by thecondensation of said hydroxyalkyl group, through a hydroxyl groupthereof, with an acylating agent. Preparative Examples are disclosed inExamples 1 and 2 (paragraphs 68 and 69). In one embodiment the amide ofa hydroxylalkyl compound is prepared by reacting glycolic acid, that is,hydroxyacetic acid, HO—CH₂—COOH with an amine.

In one embodiment the friction modifier may be a secondary or tertiaryamine being represented by the formula R⁴R⁵NR⁶, wherein R⁴ and R⁵ areeach independently an alkyl group of at least 6 carbon atoms and R⁶ ishydrogen, a hydrocarbyl group, a hydroxyl-containing alkyl group, or anamine-containing alkyl group. A more detailed description of thefriction modifier is described in U.S. Patent Application Ser. No.05/037897 in paragraphs 8 and 19 to 22.

In one embodiment the friction modifier may be derived from the reactionof a carboxylic acid or a reactive equivalent thereof with anaminoalcohol, wherein the friction modifier contains at least twohydrocarbyl groups, each containing at least 6 carbon atoms. An exampleof such a friction modifier includes the reaction product of isostearicacid or an alkyl succinic anhydride with tris-hydroxymethylaminomethane.A more detailed description of such a friction modifier is disclosed inInternational Publication WO04/007652) in paragraphs 8 and 9 to 14.

The friction modifier includes fatty amines, borated glycerol esters,fatty acid amides, non-borated fatty epoxides, borated fatty epoxides,alkoxylated fatty amines, borated alkoxylated fatty amines, metal saltsof fatty acids, fatty imidazolines, metal salts of alkyl salicylates(may also be referred to as a detergent), metal salts of sulphonates(may also be referred to as a detergent), condensation products ofcarboxylic acids or polyalkylene-polyamines, or amides of hydroxyalkylcompounds.

In one embodiment the friction modifier includes a fatty acid ester ofglycerol. The final product may be in the form of a metal salt, anamide, an imidazoline, or mixtures thereof. The fatty acids may contain6 to 24, or 8 to 18 carbon atoms. The fatty acids may branched orstraight-chain, saturated or unsaturated. Suitable acids include2-ethylhexanoic, decanoic, oleic, stearic, isostearic, palmitic,myristic, palmitoleic, linoleic, lauric, and linolenic acids, and theacids from the natural products tallow, palm oil, olive oil, peanut oil,corn oil, and Neat's foot oil. In one embodiment the fatty acid is oleicacid. When in the form of a metal salt, typically the metal includeszinc or calcium; and the products include overbased and non-overbasedproducts. Examples are overbased calcium salts and basic oleic acid-zincsalt complexes which may be represented by the general formulaZn₄Oleate₆O. When in the form of an amide, the condensation productincludes those prepared with ammonia, or with primary or secondaryamines such as diethylamine and diethanolamine. When in the form of animidazoline, the condensation product of an acid with a diamine orpolyamine such as a polyethylenepolyamine. In one embodiment thefriction modifier is the condensation product of a fatty acid with C8 toC24 atoms, and a polyalkylene polyamine, and in particular, the productof isostearic acid with tetraethylenepentamine.

In one embodiment the friction modifier includes those formed by thecondensation of the hydroxyalkyl compound with an acylating agent or anamine. A more detailed description of the hydroxyalkyl compound isdescribed in WO 2007/0044820 paragraphs 9, and 20-22. The frictionmodifier disclosed in WO2007/044820 includes an amide represented by theformula R¹²R¹³N—C(O)R¹⁴, wherein R¹² and R¹³ are each independentlyhydrocarbyl groups of at least 6 carbon atoms and R¹⁴ is a hydroxyalkylgroup of 1 to 6 carbon atoms or a group formed by the condensation ofsaid hydroxyalkyl group, through a hydroxyl group thereof, with anacylating agent. Preparative Examples are disclosed in Examples 1 and 2(paragraphs 72 and 73 of WO2007/044820). In one embodiment the amide ofa hydroxylalkyl compound is prepared by reacting glycolic acid, that is,hydroxyacetic acid, HO—CH₂—COOH with an amine.

In one embodiment the friction modifier includes a reaction product of adi-cocoalkyl amine (or di-cocoamine) with glycolic acid. The frictionmodifier includes compounds prepared in Preparative Examples 1 and 2 ofWO 2008/014319.

In one embodiment the friction modifier includes an alkoxylated alcohol.A detailed description of suitable alkoxylated alcohols is described inparagraphs 19 and 20 of US Patent Application 2005/0101497. Thealkoxylated amines are also described in U.S. Pat. No. 5,641,732 incolumn 7, line 15 to column 9, line 25.

In one embodiment the friction modifier includes a hydroxyl aminecompound as defined in column 37, line 19, to column 39, line 38 of U.S.Pat. No. 5,534,170. Optionally the hydroxyl amine includes borated assuch products are described in column 39, line 39 to column 40 line 8 ofU.S. Pat. No. 5,534,170.

In one embodiment the friction modifier includes an alkoxylated aminee.g., an ethoxylated amine derived from 1.8 % Ethomeen™ T-12 and 0.90%Tomah™ PA-1 as described in Example E of U.S. Pat. No. 5,703,023, column28, lines 30 to 46. Other suitable alkoxylated amine compounds includecommercial alkoxylated fatty amines known by the trademark “ETHOMEEN”and available from Akzo Nobel. Representative examples of theseETHOMEEN™ materials is ETHOMEEN™ C/12 (bis[2-hydroxyethyl]-coco-amine);ETHOMEEN™ C/20 (polyoxyethylene[10]cocoamine); ETHOMEEN™ S/12(bis[2-hydroxyethyl]soyamine); ETHOMEEN™ T/12(bis[2-hydroxyethyl]-tallow-amine); ETHOMEEN™T/15(polyoxyethylene-[5]tallowamine); ETHOMEEN™ 0/12(bis[2-hydroxyethyl]oleylamine); ETHOMEEN™ 18/12 (bis[2-hydroxyethyl]octadecylamine); and ETHOMEEN™ 18/25(polyoxyethylene[15]octadecylamine). Fatty amines and ethoxylated fattyamines are also described in U.S. Pat. No. 4,741,848.

In one embodiment the friction modifier includes a polyol ester asdescribed in U.S. Pat. No. 5,750,476 column 8, line 40 to column 9, line28.

In one embodiment the friction modifier includes a low potency frictionmodifier as described in U.S. Pat. No. 5,840,662 in column 2, line 28 tocolumn 3, line 26. U.S. Pat. No. 5,840,662 further discloses in column3, line 48 to column 6, line 25 specific materials and methods ofpreparing the low potency friction modifier.

In one embodiment the friction modifier includes a reaction product ofan isomerised alkenyl substituted succinic anhydride and a polyamine asdescribed in U.S. Pat. No. 5,840,663 in column 2, lines 18 to 43.Specific embodiments of the friction modifier described in U.S. Pat. No.5,840,663 are further disclosed in column 3, line 23to column 4, line35. Preparative examples are further disclosed in column 4, line 45tocolumn 5, line 37 of U.S. Pat. No. 5,840,663.

In one embodiment the friction modifier includes an alkylphosphonatemono- or di-ester sold commercially by Rhodia under the trademarkDuraphos® DMODP.

The condensation of a fatty acid and a polyamine typically result in theformation of at least one compound chosen from hydrocarbyl amides,hydrocarbyl imidazolines and mixtures thereof. In one embodiment thecondensation products are hydrocarbyl imidazolines. In one embodimentthe condensation products are hydrocarbyl amides. In one embodiment thecondensation products are mixtures of hydrocarbyl imidazolines andhydrocarbyl amides. Typically the condensation product is a mixture ofhydrocarbyl imidazolines and hydrocarbyl amides.

The fatty acid may be derived from a hydrocarbyl carboxylic acid. Thehydrocarbyl group may be alkyl, cycloalkyl, or aryl, although alkyl istypical, and the hydrocarbyl groups may be linear or branched. Typicallythe fatty acid contains 8 or more, 10 or more, more 13 or 14 or morecarbon atoms (including the carbon of the carboxy group). Typically thefatty acid contains 8 to 30, 12 to 24, or 16 to 18 carbon atoms. Othersuitable carboxylic acids may include the polycarboxylic acids orcarboxylic acids or anhydrides having from 2 to 4 carbonyl groups,typically 2. The polycarboxylic acids may include succinic acids andanhydrides and Diels-Alder reaction products of unsaturatedmonocarboxylic acids with unsaturated carboxylic acids (such as acrylic,methacrylic, maleic, fumaric, crotonic and itaconic acids). The fattycarboxylic acids include fatty monocarboxylic acids containing 8 to 30,10 to 26, or 12 to 24 carbon atoms.

Examples of suitable fatty acids may include caprylic acid, capric acid,lauric acid, myristic acid, palmitic acid, stearic acid, eicosic acidand, tall oil acids. In one embodiment the fatty acid is stearic acid,which may be used alone or in combination with other fatty acids.

One or both friction modifiers may in one embodiment benitrogen-containing compounds, typically both friction modifiers arenitrogen-containing.

In one embodiment one of friction modifiers is the condensation productof a fatty acid with C8 to C24 atoms, and a polyalkylene polyamine, andin particular, the product of isostearic acid withtetraethylenepentamine.

The phosphorus-containing compound may be a non-ionic phosphoruscompound.

In one embodiment the phosphorus-containing compounds comprise two ormore (possibly up to four) non-ionic phosphorus compounds. Typically thenon-ionic phosphorus compound may have an oxidation of +3 or +5. Thedifferent embodiments comprise phosphite ester, phosphate esters, ormixtures thereof.

In one embodiment the phosphorus-containing compound comprises anon-ionic phosphorus compound (a C₄₋₆ hydrocarbyl phosphite) and anamine salt of a phosphorus acid or ester.

The phosphorus-containing compound comprises a non-ionic phosphoruscompound that is a C₄₋₆ hydrocarbyl phosphite, or mixtures thereof. TheC₄₋₆ hydrocarbyl phosphite includes those represented by the formula:

wherein each R′″ may be independently hydrogen or a hydrocarbyl grouphaving 4 to 6carbon atoms, typically 4 carbon atoms, with the provisothat at least one of the R′″ groups is hydrocarbyl. Typically the C₄₋₆hydrocarbyl phosphite comprises dibutyl phosphite.

The C₄₋₆ hydrocarbyl phosphite may deliver at least 175 ppm, or at least200 ppm of the total amount of phosphorus delivered by thephosphorus-containing compounds.

The C₄₋₆ hydrocarbyl phosphite may deliver at least 45 wt %, or 50 wt %to 100 wt %, or 50 wt % to 90 wt % or 60 wt % to 80 wt % of the totalamount of phosphorus from the phosphorus-containing compound.

The phosphorus-containing compounds may comprise a second phosphitewhose formula is similar to that disclosed above, except R′″ may contain2 to 40, 8to 24 or 11 to 20 carbon atoms, with the proviso that thesecond phosphite is not a C₄₋₆ hydrocarbyl phosphite. Examples ofsuitable hydrocarbyl groups include propyl, dodecyl, butadecyl,hexadecyl, octadecyl, propenyl, dodecenyl, butadecenyl, hexadeencyl, oroctadecenylgroups.

As used herein the term “alk(en)yl” is intended to include moieties thathave an alkyl and/or alkenyl group.

In one embodiment the phosphorus-containing compounds include a mixtureof a C₄₋₆ hydrocarbyl phosphite (typically dibutyl phosphite) and aC₁₂₋₁₈ alk(en)yl hydrogen phosphite and optionally phosphoric acid. Indifferent embodiments the phosphoric acid is present or absent.

In one embodiment the phosphorus-containing compounds include a mixtureof a C₄₋₆ hydrocarbyl phosphite (typically dibutyl phosphite) and aC₁₆₋₁₈ alk(en)yl hydrogen phosphite. The alk(en)yl hydrogen phosphite bemay an alkyl hydrogen phosphite, and alkenyl hydrogen phosphite, or amixture of alkenyl hydrogen phosphite and alkyl hydrogen phosphite. Inone embodiment the alk(en)yl hydrogen phosphite be may a mixture ofalkenyl hydrogen phosphite and alkyl hydrogen phosphite and optionallyphosphoric acid. The phosphoric acid may be present or absent.

In one embodiment the phosphorus-containing compounds include a mixtureof a C₄₋₆ hydrocarbyl phosphite (typically dibutyl phosphite) and aC₁₁₋₁₄ alk(en)yl hydrogen phosphite. The alk(en)yl hydrogen phosphite bemay an alkyl hydrogen phosphite, and alkenyl hydrogen phosphite, or amixture of alkenyl hydrogen phosphite and alkyl hydrogen phosphite. Inone embodiment the alk(en)yl hydrogen phosphite may be a mixture ofalkenyl hydrogen phosphite and alkyl hydrogen phosphite and optionallyphosphoric acid.

In one embodiment the phosphorus-containing compounds include a mixtureof a C₄₋₆ hydrocarbyl phosphite (typically dibutyl phosphite) andphosphoric acid.

The lubricant composition in one embodiment includes a package thatcomprises a phosphorus-containing compound and a non-ionic phosphoruscompound that is a hydrocarbyl phosphite.

In one embodiment the lubricant composition further comprises a C₈₋₂₀hydrocarbyl phosphite, or a C₁₂₋₁₈ hydrocarbyl phosphite, or C₁₆₋₁₈hydrocarbyl phosphite.

In one embodiment the lubricant composition includes an amineantioxidant. The amine antioxidant may be a phenyl-α-naphthylamine(PANA) or a hydrocarbyl substituted diphenylamine, or mixtures thereof.The hydrocarbyl substituted diphenylamine may include mono- or di-C₄ toC₁₆-, or C₆ to C₁₂-, or C₉-alkyl diphenylamine. For example thehydrocarbyl substituted diphenylamine may be octyl diphenylamine, ordi-octyl diphenylamine, dinonyl diphenylamine, typically dinonyldiphenylamine.

When present the amine antioxidant may be present at 0.2 wt % to 1.2 wt%, or 0.3 wt % to 1.0 wt %, or 0.4 wt % to 0.9 wt % or 0.5 wt % to 0.8wt %, of the lubricant composition.

The lubricant composition be optionally include at least one otherantixodiant that is known and includes sulphurised olefins, hinderedphenols, molybdenum dithiocarbamates, and mixtures thereof.

The hindered phenol antioxidant often contains a secondary butyl and/ora tertiary butyl group as a sterically hindering group. The phenol groupis often further substituted with a hydrocarbyl group and/or a bridginggroup linking to a second aromatic group. Examples of suitable hinderedphenol antioxidants include 2,6-di-tert-butylphenol,4-methyl-2,6-di-tert-butylphenol, 4-ethyl-2,6-di-tert-butylphenol,4-propyl-2,6-di-tert-butylphenol or 4-butyl-2,6-di-tert-butylphenol, or4-dodecyl-2,6-di-tert-butylphenol. In one embodiment the hindered phenolantioxidant may be an ester and may include, e.g., Irganox™ L-135 fromCiba, or butyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate.

If present, the secondary antioxidant may be present at 0.1 wt % to 1 wt%, or 0.2 wt % to 0.9 wt % or 0.1 wt % to 0.4 wt %, or 0.4 wt % to 1.0wt %, of the lubricant composition.

Off-Highway Vehicle

The alkylphenol detergents described herein can be employed inoff-highway vehicles, such as, for example, farm tractors andconstruction vehicles. Such vehicles often have a common sump thatlubricates not only the transmission but also the gears, axles, andhydraulics in the vehicle. In one embodiment the invention includes alubricant composition comprising:

-   -   an oil of lubricating viscosity,    -   a dispersant typically present at 0.1 to 3 wt %, or 0.1 to 2.5        wt %, or 0.2 to 2 wt %,    -   from about 0.1 to about 5 wt % of a detergent, typically present        in an amount to deliver 10 to 2600 ppm, 100 to 2300 ppm, 200 to        2000 ppm calcium; and wherein from about 0.01 to about 2 wt %,        or from about 0.1 to about 1.75 wt %, or about 0.2 to about 1.5        wt % of the detergent comprises alkylphenol detergent described        herein.

In one embodiment the invention includes a method of lubricating anoff-highway vehicle comprising supplying to the vehicle a lubricantcomposition comprising:

-   -   an oil of lubricating viscosity,    -   a dispersant typically present at 0.1 to 3 wt %, or 0.1 to 2.5        wt %, or 0.2 to 2 wt %,    -   a phosphorus-containing antiwear agent chosen from (i) a        non-ionic phosphorus compound, which may be a hydrocarbyl        phosphite, such as a zinc dialkyldithiophosphate; or (ii) an        amine salt of a phosphorus compound,    -   from about 0.1 to about 5 wt % of a detergent, typically present        in an amount to deliver 10 to 2600 ppm, 100 to 2300 ppm, 200 to        2000 ppm calcium; and wherein from about 0.01 to about 2 wt %,        or from about 0.1 to about 1.75 wt %, or about 0.2 to about 1.5        wt % of the detergent comprises alkylphenol detergent described        herein.

The off-highway vehicle lubricated typically has a wet-brake, atransmission, a hydraulic, a final drive, a power take-off system. Theseparts are typically lubricated by a single lubricant supplied from acommon sump. The transmission may be a manual transmission or anautomatic transmission.

The calcium-containing detergent may be an overbased detergent, anon-overbased detergent, or mixtures thereof. Typically the detergentmay be overbased.

The preparation of the calcium-containing detergent is known in the art.Patents describing the preparation of overbased calcium-containingdetergents include U.S. Pat. Nos. 2,501,731; 2,616,905; 2,616,911;2,616,925; 2,777,874; 3,256,186; 3,384,585; 3,365,396; 3,320,162;3,318,809; 3,488,284; and 3,629,109.

The other detergent (other than the alkylphenol) and dispersant isdescribed above.

The phosphorus-containing antiwear agent may include zincdialkyldithiophosphate, a non-ionic phosphorus compound, which may be ahydrocarbyl phosphite; (i) a non-ionic phosphorus compound, which may bea hydrocarbyl phosphite; or (ii) an amine salt of a phosphorus compound,or mixtures thereof.

In one embodiment the lubricant composition disclosed herein contains nozinc dialkyldithiophosphate.

In one embodiment the lubricant composition disclosed herein containszinc dialkyldithiophosphate.

The phosphorus-containing compound may be a non-ionic phosphoruscompound.

In one embodiment the phosphorus-containing compounds comprise two ormore (possibly up to four) non-ionic phosphorus compounds. Typically thenon-ionic phosphorus compound may have an oxidation of +3 or +5. Thedifferent embodiments comprise phosphite ester, phosphate esters, ormixtures thereof.

In one embodiment the phosphorus-containing compound comprises anon-ionic phosphorus compound (a C₄₋₆ hydrocarbyl phosphite) and anamine salt of a phosphorus acid or ester.

The phosphorus-containing compound comprises a non-ionic phosphoruscompound that is a C₄₋₆ hydrocarbyl phosphite, or mixtures thereof. TheC₄₋₆ hydrocarbyl phosphite includes those represented by the formula:

wherein each R′″ may be independently hydrogen or a hydrocarbyl grouphaving 4 to 6 carbon atoms, typically 4 carbon atoms, with the provisothat at least one of the R′″ groups is hydrocarbyl. Typically the C₄₋₆hydrocarbyl phosphite comprises dibutyl phosphite.

The C₄₋₆ hydrocarbyl phosphite may deliver at least 175 ppm, or at least200 ppm of the total amount of phosphorus delivered by thephosphorus-containing compounds.

The C₄₋₆ hydrocarbyl phosphite may deliver at least 45 wt %, or 50 wt %to 100 wt %, or 50 wt % to 90 wt % or 60 wt % to 80 wt % of the totalamount of phosphorus from the phosphorus-containing compound.

The phosphorus-containing compounds may comprise a second phosphitewhose formula is similar to that disclosed above, except R′″ may contain2 to 40, 8 to 24 or 11 to 20 carbon atoms, with the proviso that thesecond phosphite is not a C₄₋₆ hydrocarbyl phosphite. Examples ofsuitable hydrocarbyl groups include propyl, dodecyl, butadecyl,hexadecyl, octadecyl, propenyl, dodecenyl, butadecenyl, hexadeencyl, oroctadecenylgroups.

As used herein the term “alk(en)yl” is intended to include moieties thathave an alkyl and/or alkenyl group.

In one embodiment the phosphorus-containing compounds include a mixtureof a C₄₋₆ hydrocarbyl phosphite (typically dibutyl phosphite) and aC₁₂₋₁₈ alk(en)yl hydrogen phosphite and optionally phosphoric acid. Indifferent embodiments the phosphoric acid is present or absent.

In one embodiment the phosphorus-containing compounds include a mixtureof a C₄₋₆ hydrocarbyl phosphite (typically dibutyl phosphite) and aC₁₆₋₁₈ alk(en)yl hydrogen phosphite. The alk(en)yl hydrogen phosphite bemay an alkyl hydrogen phosphite, and alkenyl hydrogen phosphite, or amixture of alkenyl hydrogen phosphite and alkyl hydrogen phosphite. Inone embodiment the alk(en)yl hydrogen phosphite be may a mixture ofalkenyl hydrogen phosphite and alkyl hydrogen phosphite and optionallyphosphoric acid. The phosphoric acid may be present or absent.

In one embodiment the phosphorus-containing compounds include a mixtureof a C₄₋₆ hydrocarbyl phosphite (typically dibutyl phosphite) and aC₁₁₋₁₄ alk(en)yl hydrogen phosphite. The alk(en)yl hydrogen phosphite bemay an alkyl hydrogen phosphite, and alkenyl hydrogen phosphite, or amixture of alkenyl hydrogen phosphite and alkyl hydrogen phosphite. Inone embodiment the alk(en)yl hydrogen phosphite may be a mixture ofalkenyl hydrogen phosphite and alkyl hydrogen phosphite and optionallyphosphoric acid.

In one embodiment the phosphorus-containing compounds include a mixtureof a C₄₋₆ hydrocarbyl phosphite (typically dibutyl phosphite) andphosphoric acid.

The lubricant composition in one embodiment includes a package thatcomprises a phosphorus-containing compound and a non-ionic phosphoruscompound that is a hydrocarbyl phosphite.

In one embodiment the lubricant composition further comprises a C₈₋₂₀hydrocarbyl phosphite, or a C₁₂₋₁₈ hydrocarbyl phosphite, or C₁₆₋₁₈hydrocarbyl phosphite, as described above.

In on embodiment the amine salt of a phosphorus acid may be derived froman amine salt of a phosphate. The amine salt of the phosphorus acid maybe represented by the formula:

wherein

-   R³ and R⁴ may be independently hydrogen or hydrocarbon typically    containing 4 to 40, or 6 to 30, or 6 to 18, or 8 to 18 carbon atoms,    with the proviso that at least one is a hydrocarbon group; and-   R^(5,) R^(6,) R⁷ and R⁸ may be independently hydrogen or a    hydrocarbyl group, with the proviso that at least one is a    hydrocarbyl group.

The hydrocarbon groups of R³ and/or R⁴ may be linear, branched, orcyclic.

Examples of a hydrocarbon group for R³ and/or R⁴ include straight-chainor branched alkyl groups include methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl.

Examples of a cyclic hydrocarbon group for R³ and/or R⁴ includecyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl,dimethylcyclopentyl, methylcyclopentyl, dimethylcyclopentyl,methylethylcyclopentyl, diethylcyclopentyl, methylcyclohexyl,dimethylcyclohexyl, methylethylcyclohexyl, diethylcyclohexyl,methylcycloheptyl, dimethyl cycloheptyl, methylethylcycloheptyl, anddiethyl cycloheptyl.

In one embodiment the phosphate may be an amine salt of a mixture ofmonoalkyl and dialkyl phosphoric acid esters. The monoalkyl and dialkylgroups may be linear or branched.

The amine salt of a phosphorus acid may be derived from an amine such asa primary amine, a secondary amine, a tertiary amine, or mixturesthereof. The amine may be aliphatic, or cyclic, aromatic ornon-aromatic, typically aliphatic. In one embodiment the amine includesan aliphatic amine such as a tertiary-aliphatic primary amine.

Examples of suitable primary amines include ethylamine, propylamine,butylamine, 2-ethylhexylamine, bis-(2-ethylhexyl)amine, octylamine, anddodecylamine, as well as such fatty amines as n-octylamine,n-decylamine, n-dodecylamine, n-tetradecylamine, n-hexadecylamine,n-octadecylamine and oleyamine. Other useful fatty amines includecommercially available fatty amines such as “Armeen®” amines (productsavailable from Akzo Chemicals, Chicago, Ill.), such as Armeen C, ArmeenO, Armeen OL, Armeen T, Armeen HT, Armeen S and Armeen SD, wherein theletter designation relates to the fatty group, such as coco, oleyl,tallow, or stearyl groups.

Examples of suitable secondary amines include dimethylamine,diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine,diheptylamine, methyl ethylamine, ethylbutyl amine,N-methyl-1-amino-cyclohexane, Armeen® 2C and ethylamylamine. Thesecondary amines may be cyclic amines such as piperidine, piperazine andmorpholine.

Examples of tertiary amines include tri-n-butylamine, tri-n-octylamine,tri-decylamine, tri-lauryl amine, tri-hexadecylamine, anddimethyloleylamine (Armeen® DMOD).

In one embodiment the amines are in the form of a mixture. Examples ofsuitable mixtures of amines include (i) a tertiary alkyl primary aminewith 11 to 14 carbon atoms, (ii) a tertiary alkyl primary amine with 14to 18 carbon atoms, or (iii) a tertiary alkyl primary amine with 18 to22 carbon atoms. Other examples of tertiary alkyl primary amines includetert-butylamine, tert-hexylamine, tert-octylamine (such as1,1-dimethylhexylamine), tert-decylamine (such as 1,1-dimethyloctylamine), tertdodecylamine, tert-tetradecylamine,tert-hexadecylamine, tert-octadecylamine, tert-tetracosanylamine, andtert-octacosanylamine.

In one embodiment a useful mixture of amines is “Primene® 81R” or“Primene® JMT.” Primene® 81R and Primene® JMT (both produced and sold byRohm & Haas) are mixtures of C11 to C14 tertiary alkyl primary aminesand C18 to C22 tertiary alkyl primary amines respectively.

The amine salt of a phosphorus acid may be prepared as is described inU.S. Pat. No. 6,468,946. Column 10, lines 15 to 63 describes phosphoricacid esters formed by reaction of phosphorus compounds, followed byreaction with an amine to form an amine salt of a phosphate hydrocarbonester. Column 10, line 64, to column 12, line 23, describes preparativeexamples of reactions between phosphorus pentoxide with an alcohol(having 4 to 13 carbon atoms), followed by a reaction with an amine(typically Primene®81-R) to form an amine salt of a phosphatehydrocarbon ester.

The sulphur-containing extreme pressure agent may be an olefin sulphide,or mixtures thereof. The olefin sulphide may include a polysulphide or asulphurised olefin such as sulphurised isobutylene, or mixtures thereof.

In one embodiment the olefin sulphide includes a polysulphide.

In one embodiment the olefin sulphide includes sulphurized isobutylene.

In one embodiment the olefin sulphide includes a mixture of asulphurised isobutylene and a polysulphide.

In one embodiment at least 50 wt % of the polysulphide molecules are amixture of tri- or tetra-sulphides. In other embodiments at least 55 wt%, or at least 60 wt % of the polysulphide molecules are a mixture oftri- or tetra-sulphides.

The polysulphide includes a sulphurised organic polysulphide from oils,fatty acids or ester, olefins or polyolefins.

Oils which may be sulfurized include natural or synthetic oils such asmineral oils, lard oil, carboxylate esters derived from aliphaticalcohols and fatty acids or aliphatic carboxylic acids (e.g., myristyloleate and oleyl oleate), and synthetic unsaturated esters orglycerides.

Fatty acids include those that contain 8 to 30, or 12 to 24 carbonatoms. Examples of fatty acids include oleic, linoleic, linolenic, andtall oil. Sulphurised fatty acid esters prepared from mixed unsaturatedfatty acid esters such as are obtained from animal fats and vegetableoils, including tall oil, linseed oil, soybean oil, rapeseed oil, andfish oil.

The polysulphide includes olefins derived from a wide range of alkenes.The alkenes typically have one or more double bonds. The olefins in oneembodiment contain 3 to 30 carbon atoms. In other embodiments, olefinscontain 3 to 16, or 3 to 9 carbon atoms. In one embodiment thesulphurised olefin includes an olefin derived from propylene,isobutylene, pentene or mixtures thereof.

In one embodiment the polysulphide comprises a polyolefin derived frompolymerising by known techniques, an olefin as described above.

In one embodiment the polysulphide includes dibutyl tetrasulphide,sulphurised methyl ester of oleic acid, sulphurised alkylphenol,sulphurised dipentene, sulphurised dicyclopentadiene, sulphurisedterpene, and sulphurised Diels-Alder adducts.

The lubricant may also include a sulphur-containing corrosion inhibitor.The sulphur-containing corrosion inhibitor may be a thiadiazolecompound, or mixtures thereof. The thiadiazole compound may includemono- or di-hydrocarbyl substituted 2,5-dimercapto-1,3,4-thiadiazolecompounds. Examples of a thiadiazole include2,5-dimercapto-1,3,4-thiadiazole, or oligomers thereof, ahydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole, ahydrocarbylthio-substituted 2,5-dimercapto-1,3,4-thiadiazole, oroligomers thereof. The oligomers of hydrocarbyl-substituted2,5-dimercapto-1,3,4-thiadiazole typically form by forming asulphur-sulphur bond between 2,5-dimercapto-1,3,4-thiadiazole units toform oligomers of two or more of said thiadiazole units. Thesethiadiazole compounds may also be used in the post treatment ofdispersants as mentioned below in the formation of adimercaptothiadiazole derivative of a polyisobutylene succinimide.

Examples of a suitable thiadiazole compound include at least one of adimercaptothiadiazole, 2,5-dimercapto-[1,3,4]-thiadiazole,3,5-dimercapto-[1,2,4]-thiadiazole, 3,4-dimercapto-[1,2,5]-thiadiazole,or 4-5-dimercapto-[1,2,3]-thiadiazole. Typically readily availablematerials such as 2,5-dimercapto-1,3,4-thiadiazole or ahydrocarbyl-substituted 2,5-dimercapto-1,3,4-thiadiazole or ahydrocarbylthio-substituted 2,5-dimercapto-1,3,4-thiadiazole arecommonly utilised.

As used herein, the term “condensation product” is intended to encompassesters, amides, imides and other such materials that may be prepared bya condensation reaction of an acid or a reactive equivalent of an acid(e.g., an acid halide, anhydride, or ester) with an alcohol or amine,irrespective of whether a condensation reaction is actually performed tolead directly to the product. Thus, for example, a particular ester maybe prepared by a transesterification reaction rather than directly by acondensation reaction. The resulting product is still considered acondensation product.

The amount of each chemical component described is presented exclusiveof any solvent or diluent oil, which may be customarily present in thecommercial material, that is, on an active chemical basis, unlessotherwise indicated. However, unless otherwise indicated, each chemicalor composition referred to herein should be interpreted as being acommercial grade material which may contain the isomers, by-products,derivatives, and other such materials which are normally understood tobe present in the commercial grade.

As used herein, the term “hydrocarbyl substituent” or “hydrocarbylgroup” is used in its ordinary sense, which is well-known to thoseskilled in the art. Specifically, it refers to a group having a carbonatom directly attached to the remainder of the molecule and havingpredominantly hydrocarbon character. Examples of hydrocarbyl groupsinclude:

hydrocarbon substituents, that is, aliphatic (e.g., alkyl or alkenyl),alicyclic (e.g., cycloalkyl, cycloalkenyl) substituents, and aromatic-,aliphatic-, and alicyclic-substituted aromatic substituents, as well ascyclic substituents wherein the ring is completed through anotherportion of the molecule (e.g., two substituents together form a ring);

substituted hydrocarbon substituents, that is, substituents containingnon-hydrocarbon groups which, in the context of this invention, do notalter the predominantly hydrocarbon nature of the substituent (e.g.,halo (especially chloro and fluoro), hydroxy, alkoxy, mercapto,alkylmercapto, nitro, nitroso, and sulfoxy);

hetero substituents, that is, substituents which, while having apredominantly hydrocarbon character, in the context of this invention,contain other than carbon in a ring or chain otherwise composed ofcarbon atoms and encompass substituents as pyridyl, furyl, thienyl andimidazolyl. Heteroatoms include sulfur, oxygen, and nitrogen. Ingeneral, no more than two, or no more than one, non-hydrocarbonsubstituent will be present for every ten carbon atoms in thehydrocarbyl group; alternatively, there may be no non-hydrocarbonsubstituents in the hydrocarbyl group.

It is known that some of the materials described above may interact inthe final formulation, so that the components of the final formulationmay be different from those that are initially added. For instance,metal ions (of, e.g., a detergent) can migrate to other acidic oranionic sites of other molecules. The products formed thereby, includingthe products formed upon employing the composition of the presentinvention in its intended use, may not be susceptible of easydescription. Nevertheless, all such modifications and reaction productsare included within the scope of the present invention; the presentinvention encompasses the composition prepared by admixing thecomponents described above.

As used herein, the term “about” means that a value of a given quantityis within ±20% of the stated value. In other embodiments, the value iswithin ±15% of the stated value. In other embodiments, the value iswithin ±10% of the stated value. In other embodiments, the value iswithin ±5% of the stated value. In other embodiments, the value iswithin ±2.5% of the stated value. In other embodiments, the value iswithin ±1% of the stated value.

Additionally, as used herein, the term “substantially” means that avalue of a given quantity is within ±10% of the stated value. In otherembodiments, the value is within ±5% of the stated value. In otherembodiments, the value is within ±2.5%) of the stated value. In otherembodiments, the value is within ±1% of the stated value.

Each of the documents referred to above is incorporated herein byreference, including any prior applications, whether or not specificallylisted above, from which priority is claimed. The mention of anydocument is not an admission that such document qualifies as prior artor constitutes the general knowledge of the skilled person in anyjurisdiction. Except in the Examples, or where otherwise explicitlyindicated, all numerical quantities in this description specifyingamounts of materials, reaction conditions, molecular weights, number ofcarbon atoms, and the like, are to be understood as modified by the word“about.” It is to be understood that the upper and lower amount, range,and ratio limits set forth herein may be independently combined.Similarly, the ranges and amounts for each element of the invention canbe used together with ranges or amounts for any of the other elements.

As used herein, the transitional term “comprising,” which is synonymouswith “including,” “containing,” or “characterized by,” is inclusive oropen-ended and does not exclude additional, un-recited elements ormethod steps. However, in each recitation of “comprising” herein, it isintended that the term also encompass, as alternative embodiments, thephrases “consisting essentially of” and “consisting of,” where“consisting of” excludes any element or step not specified and“consisting essentially of” permits the inclusion of additionalun-recited elements or steps that do not materially affect the essentialor basic and novel characteristics of the composition or method underconsideration.

While certain representative embodiments and details have been shown forthe purpose of illustrating the subject invention, it will be apparentto those skilled in this art that various changes and modifications canbe made therein without departing from the scope of the subjectinvention. In this regard, the scope of the invention is to be limitedonly by the following claims.

1. A transmission lubricant composition comprising a. an oil oflubricating viscosity, b. from about 0.1 to about 5 wt % of adispersant, and c. from about 0.1 to about 5 wt % of a detergent,wherein from about 0.01 to about 2 wt % of the detergent comprises analkylphenol detergent comprising at least one unit of analkyl-substituted phenol wherein the alkyl group is derived fromoligomers of an olefin compound containing 3 to 8 carbon atoms, whereinthe olefin-derived alkyl group comprises at least 30 mol percent ofoligomers derived from n-butane, and where the alkyl group is ahydrocarbyl group of 12 to 48 carbon atoms, and d. from about 0.05 toabout 3 wt % of a C₂-C₁₈ di- or tri-hydrocarbyl phosphite, based on thetotal weight of said lubricant wherein all wt % are based on a totalweight of said lubricant composition.
 2. The lubricant of claim 1,wherein the alkylphenol detergent is a sulfur-bridged phenate, asulfur-free alkylene-bridged phenate, a salicylate, or mixtures thereof.3. The lubricant of claim 2, wherein the alkylphenol detergent comprisesone or more alkali metals, one or more alkaline earth metals, ormixtures thereof.
 4. The lubricant of claim 3, wherein the alkylphenoldetergent is overbased.
 5. The lubricant of claim 4, where the overbasedalkylphenol detergent has a metal ratio of at least 1.5, at least 5, orat least
 7. 6. (canceled)
 7. The lubricant of claim 1, wherein thealkylphenol detergent is an overbased sulfur-coupled alkylphenoldetergent with a metal ratio of at least 1.5.
 8. The lubricant of claim1, wherein the alkylphenol detergent comprises a sulfur-bridged phenaterepresented by the structure

wherein each R is an aliphatic hydrocarbyl group derived from oligomersof n-butene, higher alphaolefins, or mixtures thereof, that contains 8to 48 carbon atoms; y is 1 to 4; and n=0 to 8, or 1 to 6, or 1 to 4, or2 to
 4. 9. The lubricant of claim 1, wherein the alkylphenol detergentis a neutral or overbased salt of alkylsalicylic acid.
 10. The lubricantof claim 1, wherein the alkylphenol detergent is an alkyl salicylaterepresented by the structure

where R is an aliphatic hydrocarbyl group derived from oligomers ofn-butene, higher alphaolefins, or mixtures thereof, and wherein thehydrocarbyl group contains 8 to 48 carbon atoms
 11. The lubricant ofclaim 1, wherein the oil of lubricating viscosity comprises at least oneAPI Group I, II, III, IV, or V, lubricant or mixtures thereof.
 12. Thelubricant of claim 1 further comprising at least one of aphosphorus-containing antiwear agent comprising a non-ionic phosphoruscompound; an amine salt of a phosphorus compound; a calcium-containingdetergent; another phenate detergent; a sulphur-containing extremepressure agent; a sulphur-containing corrosion inhibitor; orcombinations thereof.
 13. (canceled)
 14. The lubricant of claim 1further comprising less than 2000 ppm zinc based on a total weight ofsaid lubricant.
 15. The lubricant of claim 1, wherein the lubricant issubstantially free of to free of a phenol alkylated with oligomers ofpropylene.
 16. A method of lubricating a manual transmission comprisingsupplying to said manual transmission a lubricant composition comprisinga. an oil of lubricating viscosity, b. from about 0.1 to about 5 wt % ofa dispersant, and c. about 0.01 to about 2 wt % of the detergentcomprises an alkylphenol detergent comprising at least one unit of analkyl-substituted phenol wherein the alkyl group is derived fromoligomers of an olefin compound containing 3 to 8 carbon atoms, whereinthe olefin-derived alkyl group comprises at least 30 mol percent of anolefin with 4 or more carbon atoms where all wat % are based on a totalweight of said lubricant composition.
 17. The method of claim 16,wherein the lubricant composition comprises: a. the oil of lubricatingviscosity; b. a thiadiazole; c. a phosphorous containing antiwear agentd. the dispersant; e. the detergent; and f. the alkylphenol detergent.18. A method of lubricating automatic transmission comprising supplyingthe lubricant composition of claim 1 to said automatic transmission. 19.The method of claim 18, wherein the lubricant composition comprises: a.the oil of lubricating viscosity; b. a thiadiazole; c. a phosphorouscontaining antiwear agent d. the dispersant; e. the detergent; and f.the alkylphenol detergent.
 20. A method of lubricating an off-highwayvehicle comprising supplying the lubricant composition of claim 1 tosaid off-highway vehicle.
 21. The method of claim 20, wherein thelubricant composition comprises: a. the oil of lubricating viscosity; b.a zinc dialkyl dithiophosphate antiwear agent c. the dispersant; and d.the detergent.
 22. The method of claim 20, wherein the vehicle is afarm-tractor vehicle or a construction vehicle.
 23. A method oflubricating a highway vehicle comprising supplying the lubricantcomposition of claim 1 to 15 to said highway vehicle.
 24. The method ofclaim 23, wherein the lubricant composition comprises a. the oil oflubricating viscosity; b. the dispersant; c. the detergent; d. asulfurized olefin; e. a thiadiazole; and f. a phosphorous containingantiwear agent.